CN106745042B - Flyash acid system residue of aluminum-extracted prepares the method for 4A type molecular sieve and type ZSM 5 molecular sieve and the utilization method of flyash - Google Patents
Flyash acid system residue of aluminum-extracted prepares the method for 4A type molecular sieve and type ZSM 5 molecular sieve and the utilization method of flyash Download PDFInfo
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- CN106745042B CN106745042B CN201611091666.8A CN201611091666A CN106745042B CN 106745042 B CN106745042 B CN 106745042B CN 201611091666 A CN201611091666 A CN 201611091666A CN 106745042 B CN106745042 B CN 106745042B
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 192
- 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 192
- 239000010881 fly ash Substances 0.000 title claims abstract description 165
- 239000002253 acid Substances 0.000 title claims abstract description 138
- 238000000034 method Methods 0.000 title claims abstract description 118
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 152
- 239000000706 filtrate Substances 0.000 claims abstract description 147
- 229910001868 water Inorganic materials 0.000 claims abstract description 136
- 239000002893 slag Substances 0.000 claims abstract description 103
- 230000008569 process Effects 0.000 claims abstract description 46
- 238000001914 filtration Methods 0.000 claims abstract description 42
- 238000002425 crystallisation Methods 0.000 claims abstract description 30
- 238000004321 preservation Methods 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims description 111
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 104
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 89
- 229910052710 silicon Inorganic materials 0.000 claims description 74
- 239000007788 liquid Substances 0.000 claims description 73
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 65
- 239000010703 silicon Substances 0.000 claims description 62
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 56
- 229910052782 aluminium Inorganic materials 0.000 claims description 55
- 239000000377 silicon dioxide Substances 0.000 claims description 52
- 230000015572 biosynthetic process Effects 0.000 claims description 49
- 238000003786 synthesis reaction Methods 0.000 claims description 49
- 229910052593 corundum Inorganic materials 0.000 claims description 48
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 48
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 44
- 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
- 239000004411 aluminium Substances 0.000 claims description 36
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 239000000413 hydrolysate Substances 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 23
- 230000008025 crystallization Effects 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 238000009415 formwork Methods 0.000 claims description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- -1 4-propyl bromide Chemical compound 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 42
- 229910001483 soda nepheline Inorganic materials 0.000 description 35
- 239000007787 solid Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 32
- 239000011734 sodium Substances 0.000 description 28
- 238000002441 X-ray diffraction Methods 0.000 description 27
- 230000002194 synthesizing effect Effects 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 238000004090 dissolution Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 14
- 239000004115 Sodium Silicate Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000007885 magnetic separation Methods 0.000 description 11
- 238000010790 dilution Methods 0.000 description 10
- 239000012895 dilution Substances 0.000 description 10
- 238000002386 leaching Methods 0.000 description 10
- 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 9
- 239000010883 coal ash Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000002956 ash Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 7
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 7
- 239000010802 sludge Substances 0.000 description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 description 7
- 235000019795 sodium metasilicate Nutrition 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 229910020489 SiO3 Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 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 5
- 239000000446 fuel Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 229910052863 mullite Inorganic materials 0.000 description 5
- 230000020477 pH reduction Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 229910001570 bauxite Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000010117 shenhua Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005342 ion exchange 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
- 239000011707 mineral Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 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 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000269913 Pseudopleuronectes americanus Species 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/14—Type A
-
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- 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
Abstract
Field is utilized the present invention relates to flyash acid system residue of aluminum-extracted and flyash, a kind of flyash acid system residue of aluminum-extracted is disclosed and prepares the method for 4A type molecular sieve and type ZSM 5 molecular sieve and the utilization method of flyash.This method includes：(1) flyash acid system residue of aluminum-extracted is subjected to alkaline process roasting, obtains roasting slag charge；The roasting slag charge successively carries out high temperature water logging and heat preservation filtering, obtains the first filtrate；(2) first filtrate is subjected to 4A type zeolite-water thermal crystallisation, obtains 4A type molecular sieve and molecular sieve filtrate；(3) the molecular sieve filtrate is subjected to type ZSM 5 molecular sieve hydrothermal crystallizing, obtains type ZSM 5 molecular sieve and the second filtrate.It realizes consumption flyash acid system residue of aluminum-extracted, improves the utilization rate of flyash acid system residue of aluminum-extracted and the utilization of flyash.
Description
Technical field
The present invention relates to the utilization fields of flyash acid system residue of aluminum-extracted and flyash, and in particular, to a kind of flyash
Acid system residue of aluminum-extracted prepares the method for 4A type molecular sieve and type ZSM 5 molecular sieve and the utilization method of flyash.
Background technique
Aluminous fly-ash is a kind of novel bauxite resource specific to China, about 10,000,000,000 tons of aluminium oxide of Prospective resources.And
China's bauxite resource reserves that it has been established that only have 3,200,000,000 tons, and by current exploitation Quantity customizing, the resource guarantee time limit is only about
20 years, the current external dependence degree of bauxite resource was up to 55%.Therefore, the development and utilization of aluminous fly-ash are for alleviating China's alumina
Ore resources shortage ensures that China's aluminium Industrial Security and the enhancing aluminium industry capability of sustainable development have realistic meaning.
Existing developed aluminum-extracted pulverized fuel ash technique is broadly divided into three acid system, alkaline process and acid and alkali combination method major class,
Qualified alumina product is produced, but is all faced with that residue of aluminum-extracted discharge amount is big, the problem of cannot effectively dissolving in various degree.
By taking Shenhua Group " one step acid extracting of joint removal of impurities " aluminium oxide extraction process as an example, 100 tons of Al of every production2O3About 130 tons will be discharged
Residue of aluminum-extracted.The residue discharge ratio that alkaline process proposes aluminium technique is then higher.And promulgated within 2013 according to Ministry of Industry and Information《Aluminium industry is quasi-
Enter condition》Relevant regulations, the newly-built solid waste comprehensive utilization ratio using aluminous fly-ash production alumina system must reach
96% or more.Thus, it would be highly desirable to it develops the high level of residue of aluminum-extracted pulverized fuel ash, efficiently dissolve technology.
One of residue of aluminum-extracted pulverized fuel ash is noteworthy characterized by Silicon-rich (calcium) poor aluminium.Utilizing for residue of aluminum-extracted pulverized fuel ash is led at present
Concentrate on silicon systems product (waterglass, white carbon black, silicon powder etc.) preparation, basic building materials (cement, ceramic tile, steam-pressing brisk etc.) are made
It makes, and for producing the fields such as heat preservation, refractory material.Use above direction all exist in various degree product economy added value,
The contradiction of market capacity and residue utilization rate causes current residue of aluminum-extracted pulverized fuel ash overall utilization rate relatively low, and then directly limits
Application and popularization that aluminous fly-ash mentions aluminum technology are made.
Molecular sieve is a kind of material for having uniform cell structure.Due to high with adsorption capacity, thermal stability waits by force it
The unexistent advantage of its adsorbent, molecular sieve many applications such as catalysis, adsorbing separation, ion exchange obtain it is important and
It is widely applied.Work molecular sieve has higher market value, as the A type molecular sieve market price 4000 yuan -8000 yuan/ton it
Between, X-type molecular sieve price at 10,000 yuan/ton or more, type ZSM 5 molecular sieve according to its different price of silica alumina ratio be ten thousand yuan of 30-50/
Ton differs.Industrial synthesis zeolite generallys use the industrial chemicals such as waterglass, sodium aluminate or aluminium hydroxide, cost also phase
To higher.Many scholars have carried out with same type raw material (including flyash, gangue, kaolin etc.) hydrothermal synthesis molecular sieve
Research.
CN101367529B discloses a kind of method of synthesis of 4 A molecular sieve with coal ash alkali melting：By Al2O3For 36~
46%, SiO2/Al2O3The flyash that molar ratio is 1.8~2.1 is according to Na2O/Al2O3The ratio and NaOH that molar ratio is 3~10
Mixing, and remove impurity and it is levigate uniformly；By mixture in high temperature furnace 2~3h of calcining and activating at 550~600 DEG C；It will calcining
Product is dissolved in water, stirs plastic；By plastic product at 95~110 DEG C 4~6h of thermostatic crystallization, filter, wash to pH be 9~
11, drying obtains 4A molecular sieve.This method is using flyash as raw material, and this method can also generate waste material, and powder cannot be fully utilized
Silicon and aluminium in coal ash.
CN101693542A discloses a kind of production method of 4A molecular sieve, and raw material is：Flyash alkali solution technique extracts dioxy
Intermediate product sodium silicate solution or product white carbon black back dissolving obtained in SiClx production process are in lye or low modulus low concentration
The obtained sodium silicate solution of sodium silicate solution；It is intermediate obtained in flyash desiliconization ash sintering process oxygenerating aluminium production process to produce
The sodium aluminate solution that object sodium aluminate solution or product aluminium hydroxide, aluminium oxide back dissolving are obtained in the sodium aluminate solution of low modulus low concentration
Liquid；Sodium hydroxide and water；Including step：Sodium silicate solution and sodium aluminate solution removal of impurities；Sodium aluminate solution at 70~100 DEG C with
Sodium hydroxide is stirred and is sufficiently dissolved, and adds sodium silicate solution, and sodium metasilicate is added and sodium aluminate meets molar ratio SiO2:Al2O3
For 1.5~2.5, Na2O：SiO2It is 1~10, amount of water meets molar ratio H2O：Na2O is 10~80；Emulsion is stirred into, 60
1~2.5h is kept at~100 DEG C；Add directed agents；Crystallization；Crystallization product is filtered, washed, is dried, 4A molecular sieve is obtained.It should
Method is using flyash as raw material, and process is complicated, and product is single, can generate waste material, cannot be fully utilized the silicon in flyash and
Aluminium.
CN103435064A discloses a kind of method using coal ash for manufacturing for nanoscale ZSM-5 molecular sieve, including：Fine coal
Ash pretreatment；Using coal ash for manufacturing for aluminium hydroxide and sodium metasilicate；By aluminium hydroxide and sodium metasilicate and water, template tetrapropyl hydrogen
Amine-oxides mixing, microwave heating carry out hydrothermal synthesis ZSM-5 molecular sieve.The process route of the method is first to be prepared into from flyash
To aluminium hydroxide and sodium metasilicate, then synthesis of molecular sieve again, step is complicated, and can only be produced to obtain ZSM-5 type point by flyash
Son sieve.
《The residue that flyash extracts aluminum sulfate prepares 4A molecular sieve》(white light brightness etc., coal conversion, the 2nd phase of volume 32,
2009,4, p.79-82) flyash acid system residue of aluminum-extracted (below referred to as " acid sludge ") synthesis 4A molecular sieve is disclosed, wherein walking
Suddenly include：The sieving of 120 mesh is as raw material after filtering, dry and grind after acid sludge dissolution；With 10：4：15 proportion mixed raw material acid
Slag, aluminium hydroxide and sodium hydroxide；1~2h is roasted at 800~860 DEG C；Material after roasting is added into water (H2O：Na2O molar ratio
For 30), constant temperature 2h at 50~55 DEG C of temperature, control total alkalinity is 1mol/dm3；4~6h of crystallization at 90~95 DEG C；Filtration washing
Crystallization product pH=11, obtains molecular sieve.The calcium exchange quantity of products obtained therefrom is 294mg/g, has reached QB1768-93 detergent use
4A zeolites.But it is silicon source that this method, which needs the additional aluminium hydroxide that is added, is mixed and is roasted together with acid sludge.It should
Method is not complete efficiently consumption acid sludge.
《The molten fly ash residue of acid prepares 4A molecular sieve》(Yang Lin etc., Wuhan University of Technology's journal, 2012,34 (9):31-
35) with the molten fly ash residue (being about equal to flyash acid system residue of aluminum-extracted) of acid for raw material, using alkali fusion -4A points of hydro-thermal method synthesis
Son sieve.Result of study shows：Basicity 7.5, ageing for 24 hours, 90 DEG C of crystallization temperature, crystallization 4h under conditions of, can get crystallinity
Good, 1.50 μm of average grain diameter, average pore size 0.4nm, the 4A molecular sieve of calcium ion exchange capacity 305.54mg/g.But this method is not
Silicon or aluminium in " acid sludge " can be fully utilized, trash discharge can be generated, without efficiently dissolving " acid sludge ".
The method of the prior art will cause a side of the aluminium in flyash acid system residue of aluminum-extracted or silicon superfluous, need by outer
Silicon source or silicon source is added to be deployed, but this mode is unfavorable for the efficient consumption of flyash acid system residue of aluminum-extracted.
Therefore, have by preparing molecular sieve using flyash acid system residue of aluminum-extracted to realize flyash acid system residue of aluminum-extracted
The technology of consumption, which cannot be met the requirements, makes full use of sial in flyash acid system residue of aluminum-extracted, needs more effectively to utilize powder
Coal ash acid system residue of aluminum-extracted prepares molecular sieve and realizes the method that flyash acid system residue of aluminum-extracted efficiently dissolves.
Summary of the invention
The purpose of the present invention is to solve the consumptions how to be acidified residue of aluminum-extracted by preparing molecular sieve raising flyash
Efficiency, coproduction high-silicon type and low silicon type molecular sieve, and the problem of how to utilize flyash, provide a kind of flyash acid system and mention
Residue of aluminum prepares the method for 4A type molecular sieve and type ZSM 5 molecular sieve and the utilization method of flyash.
The present inventor has found that the material composition of flyash acid system residue of aluminum-extracted has compared with flyash under study for action
Its particularity：Silicone content is more enriched compared with ordinary fly ash, and aluminium content significantly reduces, and the acid-soluble element such as Fe, Mg is mentioned in acid system
It is largely removed during aluminium, wherein SiO2With Al2O3Molar ratio (can be expressed as silica alumina ratio or SiO below2/Al2O3) about
10：1.Silica alumina ratio cannot be exactly matched with high-silicon type molecular sieve, low silicon type molecular sieve in flyash acid system residue of aluminum-extracted,
If flyash acid system residue of aluminum-extracted is directly used in synthesizing low silicon molecular sieve (such as 4A type molecular sieve, silica alumina ratio are about 2~3),
Si is significantly excessive, needs additional silicon source；And when being used for synthesizing high-silicon type molecular sieve (silica alumina ratio about > 30, such as type ZSM 5 molecular sieve),
Al element is excessive, and needs additional silicon source.Obviously external silicon source or silicon source are introduced, needs additionally to consume other resources, can not have
Effect improves the utilization rate of flyash acidification residue of aluminum-extracted.On the other hand, mullite, quartz, sharp in flyash acidification residue of aluminum-extracted
The low activities such as titanium ore component is further enriched with compared with original powder coal ash, and the utilization rate that Ash Conveying is acidified residue of aluminum-extracted improves.Therefore
How rationally and preferably using silicon, the bauxite resource in flyash acidification residue of aluminum-extracted, it is not necessarily to additional silicon or aluminium, synthesis is needed to examine
Consider above-mentioned factor.The present invention is proposed to improve the consumption efficiency of flyash acidification residue of aluminum-extracted with regard to the invention people, realizes flyash
It is acidified the efficient consumption of residue of aluminum-extracted, and realizes coproduction 4A type molecular sieve and type ZSM 5 molecular sieve.
To achieve the goals above, the present invention provides a kind of flyash acid system residue of aluminum-extracted preparation 4A type molecular sieve and ZSM-
The method of 5 type molecular sieves, including：
(1) flyash acid system residue of aluminum-extracted is subjected to alkaline process roasting, obtains roasting slag charge；The roasting slag charge successively carries out
High temperature water logging and heat preservation filtering, obtain the first filtrate；
(2) first filtrate is subjected to 4A type zeolite-water thermal crystallisation, obtains 4A type molecular sieve and molecular sieve filtrate；
(3) the molecular sieve filtrate is subjected to type ZSM 5 molecular sieve hydrothermal crystallizing, obtains type ZSM 5 molecular sieve and second
Filtrate.
The present invention also provides a kind of utilization method of flyash, this method includes：Flyash progress acid system is mentioned aluminium to obtain
To flyash acid system residue of aluminum-extracted and aluminium oxide；4A type is prepared in flyash acid system residue of aluminum-extracted by means of the present invention
Molecular sieve and type ZSM 5 molecular sieve.
Through the above technical solutions, method of the invention can be realized to the silicon in flyash acid system residue of aluminum-extracted, aluminium money
The more preferable utilization in source realizes effective consumption to flyash acid system residue of aluminum-extracted, generates considerable environmental benefit；Powder is realized simultaneously
High level, the high-efficiency resource recycling of coal ash acid system residue of aluminum-extracted.
Utilization method provided by the invention to flyash acid system residue of aluminum-extracted, not needing separation and Extraction part silicon can benefit
Zeolite product is produced with silicon therein and aluminium, it is convenient to omit extracts the operation of separation.In addition, method provided by the invention can be with
Without additionally introducing external silicon source, i.e., using the abundant and efficient consumption of flyash acid system residue of aluminum-extracted.
Method of the invention is to realize the more preferable utilization of flyash acid system residue of aluminum-extracted, is particularly limited to first using low silica-alumina ratio
The synthesis of molecular sieve, can not only obtain 4A type molecular sieve, but also silicon in the adjustable filtrate generated through synthesis 4A type molecular sieve,
Aluminium ratio makes silicon, the aluminium in flyash acid system residue of aluminum-extracted to be suitble to carry out the type ZSM 5 molecular sieve of synthesizing high-silicon aluminium ratio again
Resource is fully used.The present invention dexterously using the synthesis that flyash acid system residue of aluminum-extracted is carried out to multiple molecular sieve, and
First synthesizing low silicon aluminium is limited than molecular sieve, then synthesizing high-silicon aluminium is than molecular sieve, realizing efficiently consumption flyash acid system, to mention aluminium residual
Slag and the purpose for producing high value added product again.
Method provided by the invention can also carry out flyash to utilize production aluminium oxide, 4A type molecular sieve and ZSM-5 type
Molecular sieve makes flyash be fully used, and there is no waste sludge discharges.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the flow chart of method provided by the invention.
Fig. 2 is the XRD spectra of 4A type molecular sieve prepared by the present invention.
Fig. 3 is the XRD spectra of type ZSM 5 molecular sieve prepared by the present invention.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The first object of the present invention provides a kind of flyash acid system residue of aluminum-extracted preparation 4A type molecular sieve and ZSM-5 type point
The method of son sieve, including：
(1) flyash acid system residue of aluminum-extracted is subjected to alkaline process roasting, obtains roasting slag charge；The roasting slag charge successively carries out
High temperature water logging and heat preservation filtering, obtain the first filtrate；
(2) first filtrate is subjected to 4A type zeolite-water thermal crystallisation, obtains 4A type molecular sieve and molecular sieve filtrate；
(3) the molecular sieve filtrate is subjected to type ZSM 5 molecular sieve hydrothermal crystallizing, obtains type ZSM 5 molecular sieve and second
Filtrate.
In the present invention, flyash acid system residue of aluminum-extracted is mainly contained：SiO2、Al2O3And TiO2。SiO2Content be about 70~
80 weight %, Al2O3Content be about 10~15 weight % and TiO2Content be about 3~8 weight %.Such as the Shenhua Inner Mongol
Quasi- Ge Er flyash acid system residue of aluminum-extracted, wherein SiO2Content be about 78.7 weight %, Al2O3Content be about 13.4 weights
Measure % and TiO2Content be about 5.2 weight %.Moreover, further flyash acid system residue of aluminum-extracted progress XRD analysis is shown
Show, Al2O3Substantially with mullite (3Al2O3·SiO2) form exist, TiO2Carrier is anatase and rutile；There are about 85%
Si exist as an amorphous form, remaining Si preservation in mullite and quartz in.The low activities group such as mullite, quartz, anatase
Divide and be further enriched with compared with original powder coal ash, the poor activity of silicon, aluminium element, be unfavorable for flyash acidification residue of aluminum-extracted utilizes production point
Son sieve.
According to the present invention, step (1) makes the flyash acid for handling the flyash acid system residue of aluminum-extracted
Silicon, aluminium element in method residue of aluminum-extracted can activate, and the synthesis that can more effectively participate in molecular sieve utilizes, and can rationally adjust
The content reaction raw materials requirement that meets synthesizing low silicon aluminium than molecular sieve of silicon in whole first filtrate made, aluminium element.
In step (1), the alkaline process roasting purpose is have the mineral constituent of stable crystal structure lower in mullite, quartz etc.
Maturing temperature under sufficiently decompose, make wherein Si, Al element sufficiently activated.Added by being acidified in residue of aluminum-extracted to flyash
Enter alkaline matter to be roasted together, the activation of Si, Al element may be implemented.Under preferable case, in step (1), the alkali
Method roasting process include：The flyash acid system residue of aluminum-extracted of 100 parts by weight and 100~130 parts by weight are contained into carbonic acid
Sodium material carries out mixed grinding, and obtained grinding product is crushed to again after roasting 60min~120min at 830 DEG C~890 DEG C
200 mesh are hereinafter, obtain the roasting slag charge.
In the present invention, in step (1), after completing the roasting, the product of roasting can be rapidly cooled with air,
Cooling obtains the roasting slag charge.
In the present invention, the containing sodium carbonate material be can be directly using sodium carbonate solid powder, is also possible to step
(3) the part reuse of second filtrate obtained.Main component is sodium carbonate in second filtrate, by part described second
The sodium carbonate solid that filtrate obtains after evaporative crystallization can be utilized.The flyash acid system residue of aluminum-extracted can also be mixed with
It is obtained by filtration and the first filter residue of reuse from the heat preservation.
According to the present invention, in step (1), the high temperature water logging can further leach silicon, aluminium in the roasting slag charge
Element, specifically can be with the Na in the water-soluble roasting slag charge described out2SiO3And NaAlSiO4.Under preferable case, in step (1),
The process of the high temperature water logging includes：Progress water logging is mixed with water after the roasting slag charge is removed iron, obtains water logging product；Water
Soaking temperature is 95 DEG C~105 DEG C, and the water logging time is 15min~20min；Relative to the roasting slag charge of 100g, the dosage of water
For 150~200ml.Wherein roasting slag charge removing iron can be realized by using the mode of dry magnetic separation.The high temperature
Water logging process can carry out under normal pressure or self-generated pressure.The water logging product is solidliquid mixture, and solid is the fired slags
Material is flooded dissolution Na2SiO3And NaAlSiO4Resultant product afterwards, the mineral phase composition of the product be amorphous aluminosilicates and
A small amount of crystalline state NaAlSiO4；Liquid is to contain Na2SiO3And NaAlSiO4Solution.
According to the present invention, it is further filtered by the heat preservation in step (1) and is separated by solid-liquid separation the water logging product,
And obtain first filtrate.Under preferable case, in step (1), the process of the heat preservation filtering includes：The water logging is produced
Object is diluted, filters and is rinsed with second filtrate of part, and obtained slurries are filtered to obtain the first filter residue and institute
State the first filtrate；Filtration temperature is maintained at 60 DEG C~80 DEG C.
In the case of, according to the invention it is preferred to, relative to the roasting slag charge of 100g, the dosage of second filtrate is
250~350ml.
In a kind of preferred embodiment of the invention, alkaline process roasting, high temperature water logging and the three of dilute filtration is kept the temperature
During a, the conditional parameter that is related to while when being located within above-mentioned limited range, first filter residue that can be obtained
With the smallest yield (i.e. the ratio between the first filter residue and drying matrix amount and flyash acid system residue of aluminum-extracted dry matrices amount used).Such as
This can be when not introducing external silicon and aluminum source, and flyash acid system residue of aluminum-extracted will have highest primary consumption efficiency μ.Flyash
The primary consumption efficiency μ of acid system residue of aluminum-extracted can be calculate by the following formula：
μ=[(M-M1)/(M+Mout)] × 100%；
Wherein, μ is the primary consumption efficiency of flyash acid system residue of aluminum-extracted；
M is the dry matrices amount in step (1) for the flyash acid system residue of aluminum-extracted of alkaline process roasting；
M1For the dry matrices amount of the first filter residue of gained in step (1)；
MoutDry matrices amount for the external silicon and aluminum source introduced in total overall reaction system.
Introducing without external silicon and aluminum source in the present invention, so Mout=0.
The primary consumption efficiency μ and the first filter residue M1Quality and external silicon and aluminum source MoutThe inversely proportional relationship of quality, with
Flyash acid system residue of aluminum-extracted finally dissolves efficiency direct proportionality.
In the present invention, is filtered by above-mentioned alkaline process roasting, high temperature water logging and heat preservation, flyash acid system can be made to mention aluminium residual
Silicon, aluminium element in slag switch to active component, and with Na2SiO3And NaAlSiO4Form be extracted into first filtrate.Institute
State SiO in the first filtrate2With Al2O3Molar ratio be (10~25)：1.It is preferred that SiO in first filtrate2With Al2O3Mole
Than for (12~20)：1；More preferably (12~15)：1.
In the present invention, the chemical composition (molal weight ratio) that can control first filtrate is SiO2:Al2O3:Na2O:
CO3 2-:H2O=(10~25):1:(13~20):(3.5~11):(340~430).
Silica alumina ratio in hydrothermal crystallizing mother liquor is usually deployed limit in synthesizing low silicon molecular sieve analog 4A by existing conventional techniques
It is scheduled on (2~3)：1 or so；And in synthesizing high-silicon molecular sieve analog ZSM-5, usually the silica alumina ratio in hydrothermal crystallizing mother liquor is deployed
It is limited to 30:1 or more.It is easier to synthesize pure 4A type or type ZSM 5 molecular sieve under the conditions of the silica alumina ratio of above-mentioned mother liquor.
But method provided by the invention is used to improve the consumption efficiency of flyash acid system residue of aluminum-extracted.For flyash acid
The material properties of method residue of aluminum-extracted needs to be separately added into outside if producing 4A type or type ZSM 5 molecular sieve according to routine techniques
Silicon source is to turn down silica alumina ratio to (2~3)：1, or external silicon source is added so that silica alumina ratio is turned up to 30:1 or more.And external silicon, silicon source
(i.e. Mout) introducing will result directly in flyash acid system residue of aluminum-extracted once dissolve efficiency μ reduction so that influence flyash acid
The consumption efficiency of method residue of aluminum-extracted entirety, that is, preparing the flyash acid system residue of aluminum-extracted quality that unit mass product is dissolved will drop
It is low.
In second filtrate that the present invention obtains, the concentration of sodium carbonate can be 15~25 weight %.By described second
Filtrate can reduce filtration system concentration while inhibit in the water logging product for water logging product described in dilution and filtration and washing
The hydrolysis of sodium metasilicate can be improved filter efficiency, reduce filter loss, reduce the first filter residue yield, helps to improve fine coal
The primary consumption efficiency of grey acid system residue of aluminum-extracted.At the same time, sodium carbonate recycling in systems is realized.The filtering
It can be using suction filtration or filters pressing mode.
In the case of, according to the invention it is preferred to, this method further comprises：By first filter residue, reuse is extremely after drying
Step (1) is added in the flyash acid system residue of aluminum-extracted.
According to the present invention, first filtrate synthesis 4A type molecular sieve that step (2) is obtained using step (1).And it closes
At condition make after synthesis in the obtained molecular sieve filtrate, silicon, aluminium element composition be suitble to further synthesize ZSM-5 type
Molecular sieve.Under preferable case, in step (2), the process of the 4A type zeolite-water thermal crystallisation includes：A) described first is filtered
Liquid adds water to be hydrolyzed, and obtains hydrolysate；The additional amount of water meets the roasting slag charge relative to 100g, and the hydrolysis produces
The total volume of object is 850~1000ml；B) CO is passed through into the hydrolysate2Carbon point is carried out, the pH of the hydrolysate is made
It is 12~14；C) 4A type molecular sieve seed is added or is added without in the product obtained to step b), then at 90 DEG C~110 DEG C
15~30h of hydrothermal crystallizing is carried out, 4A type molecular sieve water heat crystallization product is obtained；The dosage of the 4A type molecular sieve seed is described
Roast 0~10 weight % of slag charge；D) the 4A type molecular sieve water heat crystallization product is filtered, obtains the second filter residue and institute
State molecular sieve filtrate；Second filter residue is dried to obtain the 4A type molecular sieve.In above-mentioned synthesis process, the 4A type point
Son sieve crystal seed can be known substance, can contain the 4A type molecular sieve of the trade mark ZS-4A of Chemical Manufacture commercially available Inner Mongol day.It can be with
The XRD spectra of finally obtained solid product is measured by XRD (X-ray diffraction) method, and is compared with standard spectrogram, determining
To 4A type molecular sieve.
According to the present invention, it by the restriction in step (2) to 4A type molecular sieve water heat crystallization condition, can obtain pure
4A type molecular sieve and chemical composition are suitable for the molecular sieve filtrate of type ZSM 5 molecular sieve hydrothermal crystallizing in step (3).Step (2)
Generate the molecular sieve filtrate in, silicon, aluminium content first filtrate in generation significant changes, the preferably described molecule
SiO in sieving liquid2With Al2O3Molar ratio be (35~45)：1, more preferably (40~45)：1.In the molecular sieve filtrate
Chemical composition (molal weight ratio) can be SiO2:Al2O3:Na2O:CO3 2-:H2O=(35~45):1:(80~90):(75~
105):(2100~2300).
In the case of, according to the invention it is preferred to, in step (3), the process packet of the type ZSM 5 molecular sieve hydrothermal crystallizing
It includes：I) organic formwork agent and/or type ZSM 5 molecular sieve crystal seed are added into the molecular sieve filtrate, obtains Synthesis liquid；Ii) to
CO is passed through in the Synthesis liquid2Carbon point is carried out, the pH 9~12 of the Synthesis liquid is made；Iii) the obtained product of step ii) is existed
15~48h of hydrothermal crystallizing is carried out at 150 DEG C~190 DEG C, obtains type ZSM 5 molecular sieve hydrothermal crystallizing product；Iv) by the ZSM-
5 type molecular sieve water heat crystallization products are filtered, and obtain third filter residue and second filtrate；The third filter residue is washed
It washs, dry and roasting obtains the type ZSM 5 molecular sieve.It can be determined by XRD (X-ray diffraction) method finally obtained solid
Body is type ZSM 5 molecular sieve.
In the case of, according to the invention it is preferred to, the additional amount of the organic formwork is SiO in the Synthesis liquid23~
10mol%；The organic formwork is selected from tetrapropylammonium hydroxide (TPAOH), 4-propyl bromide (TPABr), n-propylamine and just
At least one of butylamine.In the present invention, the process of hydrothermal crystallizing can be elder generation in step (iii) when the organic formwork is added
In 120 DEG C~150 DEG C progress 2~12h of hydrothermal crystallizing, 150 DEG C~190 DEG C 5~48h of progress hydrothermal crystallizing are then heated to.
In the case of, according to the invention it is preferred to, the additional amount of the type ZSM 5 molecular sieve crystal seed is SiO in the Synthesis liquid2
3~15mol%, the SiO of the type ZSM 5 molecular sieve crystal seed2With Al2O3Molar ratio be (50~400)：1.The ZSM-5
Type molecular sieve seed can be known substance, due to alumina content highest only 3% in crystal seed, calculate shadow to the molecular weight of crystal seed
Sound is little, and it is 60 that the molecular weight that can be approximately considered crystal seed, which is the molecular weight of silica, is calculated with this and determines the ZSM-5 type
The additional amount of molecular sieve seed is SiO in the Synthesis liquid23~15mol%.The type ZSM 5 molecular sieve crystal seed can be with quotient
The type ZSM 5 molecular sieve that the trade mark purchased from Catalyst Factory, Nankai Univ production is NKF-5 is crystal seed.
According to the present invention, second filtrate, which can be improved, is utilized, under preferable case, by the one of second filtrate
During the heat preservation of part reuse to step (1) is filtered；Another part of second filtrate is evaporated crystallization
After obtaining sodium carbonate, during the alkaline process roasting of reuse to step (1).To which flyash acid system residue of aluminum-extracted can be complete
Portion is utilized, and is generated without waste.
The second object of the present invention, provides a kind of utilization method of flyash, and this method includes：Flyash is subjected to acid system
It mentions aluminium and obtains flyash acid system residue of aluminum-extracted and aluminium oxide；Flyash acid system residue of aluminum-extracted is prepared by means of the present invention
To 4A type molecular sieve and type ZSM 5 molecular sieve.
Wherein, flyash can be the fine ash that catching is got off from the flue gas after the coal combustion that coal-burning power plant is discharged.It can be with
It is to mainly contain SiO2、Al2O3And TiO2。SiO2Content be about 20~40 weight %, Al2O3Content be about 45~60 weights
Measure % and TiO2Content be about 1.5~4.5 weight %.Such as the flyash of power plant of China of Inner Mongol ancient country of Shenhua discharge, wherein
SiO2Content be about 32.43 weight %, Al2O3Content be about 50.42 weight % and TiO2Content be about 2.14 weights
Measure %.
Heretofore described acid system mentions aluminium and can adopt with method known in this field, and details are not described herein.
The present invention will be described in detail by way of examples below.
In following embodiment, by XRD (X-ray diffraction) method, penetrated using German Bruker company D8ADVANCE type X
Line diffractometer, 4 °~75 ° of the scanning (2 θ) under the conditions of 40Kv-40mA.Scanning result by with 39-0222 standard card
(PDF2004 editions) comparisons determine that obtained substance is 4A type molecular sieve；
By XRD (X-ray diffraction) method, using German Bruker company D8ADVANCE type X-ray diffractometer,
4 °~75 ° of scanning (2 θ) under the conditions of 40Kv-40mA.Scanning result with 44-0003 standard card (PDF2004 editions) by comparing
It is right, determine that obtained substance is type ZSM 5 molecular sieve.
The calculation method of the primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is as previously described.
Flyash comes from Shenhua Inner Mongol power plant of China of ancient country, and concrete composition content is as shown in table 1,
Table 1
| Composition | Al2O3 | SiO2 | P2O5 | SO3 | K2O | CaO | TiO2 | Fe2O3 | MgO | Na2O |
| Content, weight % | 50.42 | 32.43 | 0.19 | 4.0 | 0.37 | 3.03 | 2.14 | 1.71 | 0.18 | 0.03 |
Flyash acid system residue of aluminum-extracted comes autocollimatic Ge Er limited energy responsible company alumina producer, concrete composition content such as table
Shown in 2.
Table 2
| Composition | Al2O3 | SiO2 | P2O5 | SO3 | K2O | CaO | TiO2 | Fe2O3 | ZrO2 | Na2O |
| Content, weight % | 13.4 | 78.7 | 0.14 | 0.35 | 0.16 | 0.37 | 5.2 | 0.45 | 0.29 | - |
Preparation example
This preparation example illustrates that flyash acid system residue of aluminum-extracted is prepared in flyash.
Flyash 100g is taken, 5mol/L hydrochloric acid solution is added, 30min is stirred to react at 150 DEG C, filtering obtains after rinsing
Rich aluminum solutions and flyash acid system residue of aluminum-extracted.
Flyash acid system residue of aluminum-extracted chemical component is as shown in table 2.
Embodiment 1
(1) Na is added in flyash acid system residue of aluminum-extracted 50g2CO3Solid powder 60g is roasted at 860 DEG C after mixed grinding
90min, Quick air is cooling after roasting, and is crushed to about 200 mesh hereinafter, obtaining roasting slag charge；
(2) after roasting slag charge progress dry magnetic separation being removed iron, take 70g that the (roasting relative to 100g of 140ml deionized water is added
Slag material, the dosage of water are 200ml), water logging 20min is carried out under 100 DEG C and normal pressure, leaching dissolves out in roasting slag charge
Na2SiO3And NaAlSiO4, obtain the water logging product of solid-liquid mixing；Wherein solid is dissolution Na2SiO3And NaAlSiO4Afterwards surplus
Remaining product；Liquid is to contain Na2SiO3And NaAlSiO4Solution；
(3) under high-speed stirred state, whole water logging product 100g (the equivalent slag charge 70g containing roasting) is taken, is added thereto
Sodium carbonate liquor (second filtrate of the reuse from step (6), 15 weight % of concentration) 100ml is diluted, and is kept the temperature at 60 DEG C
It is filtered；Add above-mentioned second filtrate 100ml be rinsed (be equivalent to the roasting slag charge relative to 100g, above-mentioned second
Total dosage of filtrate is 286ml)；It adds a certain amount of hot water (about 80 DEG C) to be rinsed, obtains the first filter that volume is 400ml
Liquid, for synthesizing 4A type molecular sieve；The the first filter residue oven-dried weight 6.88g that will be obtained simultaneously, reuse to step (1) flyash acid system
In the alkaline process roasting of residue of aluminum-extracted；
The chemical composition (molal weight ratio) of first filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=12:1:18:9.5:
430。
(4) it takes the first filtrate 120ml (the equivalent slag charge 21.0g containing roasting) that 60ml deionized water is added to be hydrolyzed (relatively
In the roasting slag charge of 100g, the total volume of hydrolysate is 857ml)；It is passed through under stirring into obtained hydrolysate
CO2Carbon point is carried out to pH=13.455；Then the hydrolysate after carbon point is subjected to hydrothermal crystallizing 15.5h at 95 DEG C, and will
The second filter residue and molecular sieve filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further the second filter residue is rinsed, drying, is obtained
The product arrived obtains spectrogram as shown in Figure 2 through XRD analysis, compares with standard card, is determined as 4A type molecular sieve；
The chemical composition (molal weight ratio) of molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=42:1:80:75:
2100；
(5) to obtained molecular sieve filtrate 100ml be added 0.3g ZSM-5 crystal seed (Catalyst Factory, Nankai Univ, NKF-5,
SiO2/Al2O3=200, molecular weight is about that 60), obtaining Synthesis liquid, (additional amount of ZSM-5 crystal seed is SiO in Synthesis liquid2's
3mol%)；
CO is passed through into Synthesis liquid under stirring2Carbon point is carried out to pH=10.447；Then at a temperature of 180 DEG C into
Row hydrothermal crystallizing 21h, and third filter residue and the second filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further by third
Residue washing, drying, roasting, obtained product obtain spectrogram as shown in Figure 3 through XRD analysis, compare with standard card, determine
For type ZSM 5 molecular sieve；
(6) by the second filtrate, (main component is Na2CO3, the part reuse containing a small amount of Si, Al) is the carbonic acid that step (3) are added
Sodium solution, dilution and filtration and washing for water logging product；The remainder of second filtrate obtains Na after evaporative crystallization2CO3Gu
Body, reuse to step (1) flyash acid system residue of aluminum-extracted alkaline process roasting in.
The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 86.24%；First filter residue can be recognized after recycling
It is approximately 100% for the whole consumption efficiency of flyash acid system residue of aluminum-extracted.
Embodiment 2
(1) Na is added in flyash acid system residue of aluminum-extracted 50g2CO3Solid powder 65g is roasted at 890 DEG C after mixed grinding
60min, Quick air is cooling after roasting, and is crushed to about 200 mesh hereinafter, obtaining roasting slag charge；
(2) after roasting slag charge progress dry magnetic separation being removed iron, take 70g that the (roasting relative to 100g of 105ml deionized water is added
Slag material, the dosage of water are 150ml), water logging 18min is carried out under 95 DEG C and normal pressure, leaching dissolves out in roasting slag charge
Na2SiO3And NaAlSiO4, obtain the water logging product of solid-liquid mixing；Wherein, solid is dissolution Na2SiO3And NaAlSiO4Afterwards surplus
Remaining product；Liquid is to contain Na2SiO3And NaAlSiO4Solution.
(3) under high-speed stirred state, whole water logging product 93g (the equivalent slag charge 70g containing roasting) is taken, carbon is added thereto
Acid sodium solution (second filtrate of the reuse from step (6), 20 weight % of concentration) 100ml is diluted, and keep the temperature at 80 DEG C into
Row filters；It adds above-mentioned second filtrate 100ml and is rinsed and (be equivalent to the roasting slag charge relative to 100g, above-mentioned second filter
Total dosage of liquid adds a certain amount of hot water (about 90 DEG C) for 286ml) and is rinsed, and obtains the first filtrate that volume is 400ml,
For synthesizing 4A type molecular sieve；The the first filter residue oven-dried weight 6.63g that will be obtained simultaneously, reuse to step (1) flyash acid system mention
In the alkaline process roasting of residue of aluminum；
The chemical composition (molal weight ratio) of first filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=13.4:1:18:
9.5:420。
(4) it takes the first filtrate 120ml (the equivalent slag charge 21.0g containing roasting) that 60ml deionized water is added to be hydrolyzed (relatively
In the roasting slag charge of 100g, the total volume of hydrolysate is 857ml)；It is passed through under stirring into obtained hydrolysate
CO2Carbon point is carried out to pH=13.567；Then hydrolysate after carbon point is added to the 4A type molecular sieve seed (Inner Mongol of 0.2g
Day contain chemical industry, ZS-4A), then hydrothermal crystallizing 20h is carried out at 110 DEG C, and obtained hydrothermal crystallizing product is obtained by filtration the
Two filter residues and molecular sieve filtrate；Further the second filter residue is rinsed, drying, obtained product obtains spectrogram and mark through XRD analysis
Quasi- card comparison, is determined as 4A type molecular sieve；
The chemical composition (molal weight ratio) of molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=41:1:88.5:
83:2170；
(5) to obtained molecular sieve filtrate 100ml be added 0.3g ZSM-5 crystal seed (Catalyst Factory, Nankai Univ, NKF-5,
SiO2/Al2O3=400, molecular weight is about that 60), obtaining Synthesis liquid, (additional amount of ZSM-5 crystal seed is SiO in Synthesis liquid2's
3mol%)；
CO is passed through into Synthesis liquid under stirring2Carbon point is carried out to pH=10.447；Then at a temperature of 150 DEG C into
Row hydrothermal crystallizing 48h, and third filter residue and the second filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further by third
Residue washing, drying, roasting, obtained product obtain spectrogram and standard card compare, be determined as ZSM-5 type point through XRD analysis
Son sieve；
(6) by the second filtrate, (main component is Na2CO3, the part reuse containing a small amount of Si, Al) is the carbonic acid that step (3) are added
Sodium solution, dilution and filtration and washing for water logging product；The remainder of second filtrate obtains Na after evaporative crystallization2CO3Gu
Body, reuse to step (1) flyash acid system residue of aluminum-extracted alkaline process roasting in.
The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 86.74%；First filter residue can be recognized after recycling
It is approximately 100% for the whole consumption efficiency of flyash acid system residue of aluminum-extracted.
Embodiment 3
(1) Na is added in flyash acid system residue of aluminum-extracted 50g2CO3Solid powder 50g is roasted at 830 DEG C after mixed grinding
120min, Quick air is cooling after roasting, and is crushed to about 200 mesh hereinafter, obtaining roasting slag charge；
(2) after roasting slag charge progress dry magnetic separation being removed iron, take 70g that the (roasting relative to 100g of 130ml deionized water is added
Slag material, the dosage of water are 186ml) water logging 15min is carried out under 105 DEG C and normal pressure, leaching dissolves out in roasting slag charge
Na2SiO3And NaAlSiO4, obtain the water logging product of solid-liquid mixing；Wherein solid is dissolution Na2SiO3And NaAlSiO4Afterwards surplus
Remaining product；Liquid is to contain Na2SiO3And NaAlSiO4Solution；
(3) under high-speed stirred state, whole water logging product 96g (the equivalent slag charge 70g containing roasting) is taken, carbon is added thereto
Acid sodium solution (second filtrate of the reuse from step (6), 25 weight % of concentration) 100ml is diluted, and keep the temperature at 70 DEG C into
Row filters；It adds above-mentioned second filtrate 100ml and is rinsed and (be equivalent to the roasting slag charge relative to 100g, above-mentioned second filter
Total dosage of liquid is 286ml)；It adds a certain amount of hot water (about 70 DEG C) to be rinsed, obtains the first filter that volume is 400ml
Liquid, for synthesizing 4A type molecular sieve；The the first filter residue oven-dried weight 6.50g that will be obtained simultaneously, reuse to step (1) flyash acid system
In the alkaline process roasting of residue of aluminum-extracted；
The chemical composition (molal weight ratio) of first filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=14.8:1:19.9:
10.5:353。
(4) it takes the first filtrate 120ml (the equivalent slag charge 18.0g containing roasting) that 60ml deionized water is added to be hydrolyzed (relatively
In the roasting slag charge of 100g, the total volume of hydrolysate is 960ml)；It is passed through under stirring into obtained hydrolysate
CO2Carbon point is carried out to pH=12.54；Then hydrolysate after carbon point is added to the 4A type molecular sieve seed (ZS- of 0.27g
4A), then at 105 DEG C hydrothermal crystallizing 18h is carried out, and the second filter residue and molecule is obtained by filtration in obtained hydrothermal crystallizing product
Sieving liquid；Further the second filter residue being rinsed, drying, obtained product obtains spectrogram and standard card compares through XRD analysis,
It is determined as 4A type molecular sieve；
The chemical composition (molal weight ratio) of molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=41:1:87:
102:2155；
(5) to obtained molecular sieve filtrate 100ml be added 0.5g ZSM-5 crystal seed (Catalyst Factory, Nankai Univ, NKF-5,
SiO2/Al2O3=50, molecular weight is about that 60), obtaining Synthesis liquid, (additional amount of ZSM-5 crystal seed is SiO in Synthesis liquid2's
5mol%)；
CO is passed through into Synthesis liquid under stirring2Carbon point is carried out to pH=9.5；Then it is carried out at a temperature of 190 DEG C
Hydrothermal crystallizing 15h, and third filter residue and the second filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further third is filtered
Wash heat is washed, dries, is roasted, and obtained product obtains spectrogram and standard card compares, be determined as ZSM-5 type molecule through XRD analysis
Sieve；
(6) by the second filtrate, (main component is Na2CO3, the part reuse containing a small amount of Si, Al) is the described of addition step (3)
Sodium carbonate liquor, dilution and filtration and washing for water logging product；The remainder of second filtrate obtains after evaporative crystallization
Na2CO3Solid, reuse to step (1) flyash acid system residue of aluminum-extracted alkaline process roasting in.
The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 87.0%；First filter residue is after recycling, it is believed that
The whole consumption efficiency of flyash acid system residue of aluminum-extracted is approximately 100%.
Embodiment 4
(1) Na is added in flyash acid system residue of aluminum-extracted 50g2CO3Solid powder 65g is roasted at 890 DEG C after mixed grinding
60min, Quick air is cooling after roasting, and is crushed to about 180 mesh hereinafter, obtaining roasting slag charge；
(2) roasting slag charge is subjected to dry magnetic separation except after iron, taking 70g that 105ml deionized water is added under 95 DEG C and normal pressure
Carry out water logging 18min, the Na in leaching dissolution roasting slag charge2SiO3And NaAlSiO4, obtain the water logging product of solid-liquid mixing；Its
Middle solid is dissolution Na2SiO3And NaAlSiO4Resultant product afterwards；Liquid is to contain Na2SiO3And NaAlSiO4Solution；
(3) under high-speed stirred state, whole water logging product 93g (the equivalent slag charge 70g containing roasting) is taken, carbon is added thereto
Acid sodium solution (second filtrate of the reuse from step (6), 20 weight % of concentration) 100ml is diluted, and keep the temperature at 80 DEG C into
Row filters；Above-mentioned second filtrate 100ml is added to be rinsed；Relative to the roasting slag charge of 100g, total dosage of the second filtrate
For 286ml)；It adds a certain amount of hot water (about 90 DEG C) to be rinsed, the first filtrate that volume is 400ml is obtained, for synthesizing
4A type molecular sieve；The the first filter residue oven-dried weight 6.63g that will be obtained simultaneously, reuse to step (1) flyash acid system residue of aluminum-extracted
In alkaline process roasting；
The chemical composition (molal weight ratio) of first filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=13.4:1:18:
9.5:420。
(4) take the first filtrate 120ml (containing roasting slag charge 21.0g) be added 80ml deionized water be hydrolyzed (relative to
The roasting slag charge of 100g, the total volume of hydrolysate are 952ml)；CO is passed through into obtained hydrolysate under stirring2
Carbon point is carried out to pH=13.567；Then hydrolysate after carbon point is added to the 4A type molecular sieve seed (ZS-4A) of 0.2g, then
Hydrothermal crystallizing 20h is carried out at 110 DEG C, and the second filter residue and molecule sieving is obtained by filtration in obtained hydrothermal crystallizing product
Liquid；Further the second filter residue is rinsed, drying, obtained product obtains spectrogram and standard card compares, determine through XRD analysis
For 4A type molecular sieve；
The chemical composition (molal weight ratio) of molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=41:1:88.5:
83:2260；
(5) TPAOH (25 weight % aqueous solution) template (traditional Chinese medicines of 10.0g are added to obtained molecular sieve filtrate 100ml
Group's reagent) obtaining Synthesis liquid, (additional amount of TPAOH is SiO in Synthesis liquid22.5mol%)；
CO is passed through into Synthesis liquid under stirring2Carbon point is carried out to pH=10.106；Then first at a temperature of 140 DEG C
Hydrothermal crystallizing 2h is carried out, then is warming up to 180 DEG C of progress hydrothermal crystallizing 15.7h, and by obtained hydrothermal crystallizing product through filtering
To third filter residue and the second filtrate；Further by third residue washing, drying, roasting, obtained product is obtained through XRD analysis
Spectrogram and standard card compare, and are determined as type ZSM 5 molecular sieve；
(6) by the second filtrate, (main component is Na2CO3, the part reuse containing a small amount of Si, Al) is the described of addition step (3)
Sodium carbonate liquor, dilution and filtration and washing for water logging product；The remainder of second filtrate obtains after evaporative crystallization
Na2CO3Solid, reuse to step (1) flyash acid system residue of aluminum-extracted alkaline process roasting in.
The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 86.74%；First filter residue can be recognized after recycling
It is approximately 100% for the whole consumption efficiency of flyash acid system residue of aluminum-extracted.
Embodiment 5
(1) Na is added in flyash acid system residue of aluminum-extracted 50g2CO3Solid powder 60g is roasted at 860 DEG C after mixed grinding
90min, Quick air is cooling after roasting, and is crushed to about 200 mesh hereinafter, obtaining roasting slag charge；
(2) roasting slag charge is subjected to dry magnetic separation except after iron, taking 70g that 140ml deionized water is added under 100 DEG C and normal pressure
Carry out water logging 20min, the Na in leaching dissolution roasting slag charge2SiO3And NaAlSiO4, obtain the water logging product of solid-liquid mixing；Its
Middle solid is dissolution Na2SiO3And NaAlSiO4Resultant product afterwards；Liquid is to contain Na2SiO3And NaAlSiO4Solution；
(3) under high-speed stirred state, whole water logging product 100g (the equivalent slag charge 70g containing roasting) is taken, is added thereto
Sodium carbonate liquor (second filtrate of the reuse from step (6), 25 weight % of concentration) 100ml is diluted, and is kept the temperature at 60 DEG C
It is filtered；Add above-mentioned second filtrate 100ml be rinsed (be equivalent to the roasting slag charge relative to 100g, above-mentioned second
Total dosage of filtrate is 286ml)；It adds a certain amount of hot water (about 80 DEG C) to be rinsed, obtains the first filter that volume is 400ml
Liquid, for synthesizing 4A type molecular sieve；The the first filter residue oven-dried weight 6.88g that will be obtained simultaneously, reuse to step (1) flyash acid system
In the alkaline process roasting of residue of aluminum-extracted；
The chemical composition (molal weight ratio) of first filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=12:1:18:9.5:
430。
(4) it takes the first filtrate 120ml (the equivalent slag charge 21.0g containing roasting) that 60ml deionized water is added to be hydrolyzed (relatively
In the roasting slag charge of 100g, the total volume of hydrolysate is 857ml)；It is passed through under stirring into obtained hydrolysate
CO2Carbon point is carried out to pH=13.455；Then the hydrolysate after carbon point is subjected to hydrothermal crystallizing 15.5h at 95 DEG C, and will
The second filter residue and molecular sieve filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further the second filter residue is rinsed, drying, is obtained
The product arrived obtains spectrogram and standard card compares, be determined as 4A type molecular sieve through XRD analysis；
The chemical composition (molal weight ratio) of molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=42:1:80:75:
2100。
(5) to obtained molecular sieve filtrate 100ml be added 0.1g ZSM-5 crystal seed (Catalyst Factory, Nankai Univ, NKF-5,
SiO2/Al2O3=200, molecular weight is about that 60), obtaining Synthesis liquid, (additional amount of ZSM-5 crystal seed is SiO in Synthesis liquid2's
15mol%)；
CO is passed through into Synthesis liquid under stirring2Carbon point is carried out to pH=11.03；Then at a temperature of 180 DEG C into
Row hydrothermal crystallizing 20h, and third filter residue and the second filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further by third
Residue washing, drying, roasting, obtained product obtain spectrogram and standard card compare, be determined as ZSM-5 type point through XRD analysis
Son sieve；
(6) by the second filtrate, (main component is Na2CO3, the part reuse containing a small amount of Si, Al) is the described of addition step (3)
Sodium carbonate liquor, dilution and filtration and washing for water logging product；The remainder of second filtrate obtains after evaporative crystallization
Na2CO3Solid, reuse to step (1) flyash acid system residue of aluminum-extracted alkaline process roasting in.
The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 86.24%；First filter residue can be recognized after recycling
It is approximately 100% for the whole consumption efficiency of flyash acid system residue of aluminum-extracted.
Embodiment 6
(1) Na is added in flyash acid system residue of aluminum-extracted 50g2CO3Solid powder 65g is roasted at 890 DEG C after mixed grinding
60min, Quick air is cooling after roasting, and is crushed to about 180 mesh hereinafter, obtaining roasting slag charge；
(2) roasting slag charge is subjected to dry magnetic separation except after iron, taking 70g that 105ml deionized water is added under 95 DEG C and normal pressure
Carry out water logging 18min, the Na in dissolution roasting slag charge2SiO3And NaAlSiO4, obtain the water logging product of solid-liquid mixing；It is wherein solid
Body is dissolution Na2SiO3And NaAlSiO4Resultant product afterwards；Liquid is to contain Na2SiO3And NaAlSiO4Solution；
(3) under high-speed stirred state, whole water logging product 93g (the equivalent slag charge 70g containing roasting) is taken, carbon is added thereto
Acid sodium solution (second filtrate of the reuse from step (6), 20 weight % of concentration) 100ml is diluted, and keep the temperature at 80 DEG C into
Row filters；It adds above-mentioned second filtrate 100ml and is rinsed and (be equivalent to the roasting slag charge relative to 100g, above-mentioned second filter
Total dosage of liquid is 286ml)；It adds a certain amount of hot water (about 90 DEG C) to be rinsed, obtains the first filter that volume is 400ml
Liquid, for synthesizing 4A type molecular sieve；The the first filter residue oven-dried weight 6.88g that will be obtained simultaneously, reuse to step (1) flyash acid system
In the alkaline process roasting of residue of aluminum-extracted；
The chemical composition (molal weight ratio) of first filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=13.4:1:18:
9.5:420。
(4) it takes the first filtrate 120ml (the equivalent slag charge 21.0g containing roasting) that 60ml deionized water is added to be hydrolyzed (relatively
In the roasting slag charge of 100g, the total volume of hydrolysate is 857ml)；It is passed through under stirring into obtained hydrolysate
CO2Carbon point is carried out to pH=13.567；Then hydrolysate after carbon point is added to the 4A type molecular sieve seed (ZS- of 0.2g
4A), then at 110 DEG C hydrothermal crystallizing 20h is carried out, and the second filter residue and molecule is obtained by filtration in obtained hydrothermal crystallizing product
Sieving liquid；Further the second filter residue being rinsed, drying, obtained product obtains spectrogram and standard card compares through XRD analysis,
It is determined as 4A type molecular sieve；
The chemical composition (molal weight ratio) of molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=41:1:88.5:
83:2170；
(5) to the cetyl trimethylammonium bromide of obtained molecular sieve filtrate 100ml addition 0.9g, (25 weight % are water-soluble
Liquid) template (Chinese medicines group reagent) obtain Synthesis liquid (additional amount of cetyl trimethylammonium bromide be Synthesis liquid in SiO2
2.5mol%)；
CO is passed through into Synthesis liquid under stirring2Carbon point is carried out to pH=10.54；Then first at a temperature of 120 DEG C
Hydrothermal crystallizing 12h is carried out, then is warming up to 150 DEG C of progress hydrothermal crystallizing 48h, and by obtained hydrothermal crystallizing product through being obtained by filtration
Third filter residue and the second filtrate；Further by third residue washing, drying, roasting, obtained product is composed through XRD analysis
Figure is compared with standard card, is determined as type ZSM 5 molecular sieve；
(6) by the second filtrate, (main component is Na2CO3, the part reuse containing a small amount of Si, Al) is the described of addition step (3)
Sodium carbonate liquor, dilution and filtration and washing for water logging product；The remainder of second filtrate obtains after evaporative crystallization
Na2CO3Solid, reuse to step (1) flyash acid system residue of aluminum-extracted alkaline process roasting in.
The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 86.24%；First filter residue can be recognized after recycling
It is approximately 100% for the whole consumption efficiency of flyash acid system residue of aluminum-extracted.
Comparative example 1
(1) Na is added in flyash acid system residue of aluminum-extracted 50g2CO3Solid powder 60g is roasted at 860 DEG C after mixed grinding
90min, Quick air is cooling after roasting, and is crushed to about 200 mesh hereinafter, obtaining roasting slag charge；
(2) after roasting slag charge progress dry magnetic separation being removed iron, take 70g that the (roasting relative to 100g of 700ml deionized water is added
Slag material, the dosage of water are 1000ml), water logging 40min is carried out under 100 DEG C and normal pressure, leaching dissolves out in roasting slag charge
Na2SiO3And NaAlSiO4, obtain the water logging product of solid-liquid mixing；Wherein solid is dissolution part Na2SiO3And NaAlSiO4Afterwards
Resultant product；Liquid is to contain Na2SiO3And NaAlSiO4Solution；
(3) under high-speed stirred state, whole water logging product 650g (the equivalent slag charge 70g containing roasting) is taken, is kept the temperature at 60 DEG C
Under filtered, the sodium carbonate liquor 100ml for adding 15 weight %, which is rinsed, (is equivalent to the fired slags relative to 100g
Material, total dosage of above-mentioned sodium carbonate liquor are 286ml)；A certain amount of hot water (about 80 DEG C) is added to be rinsed, first obtained
Filter residue oven-dried weight 22.45g, is computed, and it is only 55.10% that flyash acid system residue of aluminum-extracted, which once dissolves efficiency μ,.
Comparative example 1 high-temperature water leaching during be added water dosage it is excessive, be more than it is of the invention limit relative to 100g
The roasting slag charge, the dosage of water is the liquid-solid ratio range of 150~200ml, causes the basicity of water logging product to reduce, silicon, aluminium
Dissolution rate it is seriously relatively low, the first filter residue yield is higher, is not able to achieve the target that flyash acid system residue of aluminum-extracted efficiently dissolves.
Comparative example 2
(1) Na is added in flyash acid system residue of aluminum-extracted 50g2CO3Solid powder 60g is roasted at 860 DEG C after mixed grinding
90min, Quick air is cooling after roasting, and is crushed to about 200 mesh hereinafter, obtaining roasting slag charge；
(2) after roasting slag charge progress dry magnetic separation being removed iron, take 70g that the (roasting relative to 100g of 140ml deionized water is added
Slag material, the dosage of water are 200ml), water logging 20min is carried out under 100 DEG C and normal pressure, leaching dissolves out in roasting slag charge
Na2SiO3And NaAlSiO4, obtain the water logging product of solid-liquid mixing；Wherein solid is dissolution Na2SiO3And NaAlSiO4Afterwards surplus
Remaining product；Liquid is to contain Na2SiO3And NaAlSiO4Solution；
(3) under high-speed stirred state, whole water logging product 100g (the equivalent slag charge 70g containing roasting) is taken, is added thereto
Boiling water 100ml is diluted, and keep the temperature filtered at 60 DEG C, add boiling water 100ml be rinsed (be equivalent to relative to
The roasting slag charge of 100g, the addition total amount of boiling water are 286ml)；It adds a certain amount of hot water (about 80 DEG C) to be rinsed, obtains body
Product is the first filtrate of 400ml, for synthesizing 4A type molecular sieve；The the first filter residue oven-dried weight 17.35g that will be obtained simultaneously, reuse
Into the alkaline process roasting of step (1) flyash acid system residue of aluminum-extracted；
The chemical composition (molal weight ratio) of first filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=8.3:1:10:6.5:
430。
(4) 4A type molecular sieve is directly synthesized using first filtrate, the hydrothermal crystallizing 15.5h at 95 DEG C, and will obtain
Hydrothermal crystallizing product solid product is obtained by filtration.
Obtained solid product detects the mixture consisting of amorphous aluminosilicate and multiple types molecular sieve through XRD,
Pure 4A type molecular sieve can not be obtained.
Using boiling water water logging product is diluted in comparative example 2 and filtration and washing, and does not use sodium carbonate liquor, caused
The highly hydrolyzed hydrated SiO 2 for generating solid phase occurs in dilution and filter process for Si element in water logging product liquid phase, thus
Serious filter loss is generated, the first filter residue yield is caused to be sharply increased, flyash acid system residue of aluminum-extracted once dissolves efficiency μ drop
Down to 65.3%.Meanwhile hydrothermal crystallizing is directly carried out according to conventional hydrothermal crystallization condition using the first filtrate, fail to obtain pure
4A type molecular sieve.
In addition, step (1)-(3) can not also obtain the synthesis mother liquid for being suitable for synthesizing type ZSM 5 molecular sieve, cannot get pure
Net type ZSM 5 molecular sieve.Tail washings or molecular sieve filtrate main component after synthesis 4A type molecular sieve are sodium carbonate, are contained only
There are micro Si, Al, cannot act as silicon source or silicon source and further synthesize any other types of molecules sieve.
Comparative example 3
(1) Na is added in flyash acid system residue of aluminum-extracted 50g2CO3Solid powder 65g is roasted at 890 DEG C after mixed grinding
60min, Quick air is cooling after roasting, and is crushed to about 200 mesh hereinafter, obtaining roasting slag charge；
(2) after roasting slag charge progress dry magnetic separation being removed iron, take 70g that the (roasting relative to 100g of 140ml deionized water is added
Slag material, the dosage of water are 200ml), water logging 20min is carried out under 100 DEG C and normal pressure, leaching dissolves out in roasting slag charge
Na2SiO3And NaAlSiO4, obtain the water logging product of solid-liquid mixing；Wherein solid is dissolution Na2SiO3And NaAlSiO4Afterwards surplus
Remaining product；Liquid is to contain Na2SiO3And NaAlSiO4Solution；
(3) under high-speed stirred state, whole water logging product 100g (the equivalent slag charge 70g containing roasting) is taken, is added thereto
Sodium carbonate liquor (second filtrate of the reuse from step (5), 15 weight % of concentration) 100ml is diluted, and is kept the temperature at 60 DEG C
Filtered, add above-mentioned second filtrate 100ml be rinsed (be equivalent to the roasting slag charge relative to 100g, above-mentioned second
Total dosage of filtrate is 286ml)；It adds a certain amount of hot water (about 80 DEG C) to be rinsed, obtains the first filter that volume is 400ml
Liquid, for synthesizing 4A type molecular sieve；The the first filter residue oven-dried weight 6.88g that will be obtained simultaneously, reuse to step (1) flyash acid system
In the alkaline process roasting of residue of aluminum-extracted；
The chemical composition (molal weight ratio) of first filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=12:1:18:9.5:
430。
(4) it takes the first filtrate whole 400ml (the equivalent slag charge 70.0g containing roasting) that 200ml deionized water is added to be hydrolyzed
(relative to the roasting slag charge of 100g, the total volume of hydrolysate is 857ml)；Sodium metaaluminate (NaAlO is added again2) solid
41.0g, is configured to 4A type molecular sieve synthesis mother liquid, and chemical composition (molal weight ratio) is SiO2:Al2O3:Na2O:CO3 2-:H2O
=12:6:21.3:9.5:652.
CO is passed through into obtained hydrolysate under stirring2Carbon point is carried out to pH=13.455；Then by carbon point
Hydrolysate afterwards carries out hydrothermal crystallizing 15.5h at 95 DEG C, and the second filter is obtained by filtration in obtained hydrothermal crystallizing product
Slag and the second filtrate；Further the second filter residue is rinsed, drying, obtained product obtains spectrogram and standard card through XRD analysis
Comparison, is determined as 4A type molecular sieve；
(main component is Na to (5) second filtrates2CO3, only it is the carbon that step (3) are added containing a small amount of Si, Al) part reuse
Acid sodium solution, dilution and filtration and washing for water logging product；The remainder of second filtrate obtains Na after evaporative crystallization2CO3
Solid, reuse to step (1) flyash acid system residue of aluminum-extracted alkaline process roasting in.
According to being formulated conventionally 4A type molecular sieve synthesis mother liquid in comparative example 3, but need additional silicon source sodium metaaluminate (Mout
=41.0g) adjustment silica alumina ratio, as a result the primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is only 47.38%；And it obtains
The second filtrate also can not continue to prepare type ZSM 5 molecular sieve as silicon source or silicon source, i.e. products obtained therefrom only has 4A type molecular sieve
It is a kind of.
Comparative example 4
(1) Na is added in flyash acid system residue of aluminum-extracted 50g2CO3Solid powder 65g is roasted at 890 DEG C after mixed grinding
60min, Quick air is cooling after roasting, and is crushed to about 200 mesh hereinafter, obtaining roasting slag charge；
(2) after roasting slag charge progress dry magnetic separation being removed iron, take 70g that the (roasting relative to 100g of 140ml deionized water is added
Slag material, the dosage of water are 200ml), water logging 20min is carried out under 100 DEG C and normal pressure, leaching dissolves out in roasting slag charge
Na2SiO3And NaAlSiO4, obtain the water logging product of solid-liquid mixing；Wherein solid is dissolution Na2SiO3And NaAlSiO4Afterwards surplus
Remaining product；Liquid is to contain Na2SiO3And NaAlSiO4Solution；
(3) under high-speed stirred state, whole water logging product 100g (the equivalent slag charge 70g containing roasting) is taken, is added thereto
Sodium carbonate liquor (second filtrate of the reuse from step (6), 15 weight % of concentration) 100ml is diluted, and is kept the temperature at 60 DEG C
It is filtered；Add above-mentioned second filtrate 100ml be rinsed (be equivalent to the roasting slag charge relative to 100g, above-mentioned second
Total dosage of filtrate is 286ml)；It adds a certain amount of hot water (about 80 DEG C) to be rinsed, obtains the first filter that volume is 400ml
Liquid, for synthesizing 4A type molecular sieve；The the first filter residue oven-dried weight 6.88g that will be obtained simultaneously, reuse to step (1) flyash acid system
In the alkaline process roasting of residue of aluminum-extracted；
The chemical composition (molal weight ratio) of first filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=12:1:18:9.5:
430。
(4) it takes the first filtrate whole 400ml (the equivalent slag charge 70.0g containing roasting) that 1500ml deionized water is added to be hydrolyzed
(relative to the roasting slag charge of 100g, the total volume of hydrolysate is 2143ml)；Sodium metasilicate (Na is added again2SiO3) solid
201.3g, as the hydrothermal crystallizing mother liquor of type ZSM 5 molecular sieve after being completely dissolved, chemical composition (molal weight ratio) is
SiO2:Al2O3:Na2O:CO3 2-:H2O=45:1:51:35:2100.
(5) ZSM-5 crystal seed (Catalyst Factory, Nankai Univ, the NKF- of 0.3g are added to obtained hydrothermal crystallizing mother liquor 100ml
5, molal weight ratio SiO2/Al2O3=200, molecular weight is about that 60), obtaining Synthesis liquid, (additional amount of ZSM-5 crystal seed is Synthesis liquid
Middle SiO23mol%)；
CO is passed through into Synthesis liquid under stirring2Carbon point is carried out to pH=10.447；Then at a temperature of 180 DEG C into
Row hydrothermal crystallizing 21h, and third filter residue and the second filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further by third
Residue washing, drying, roasting, obtained product obtain spectrogram and standard card compare, be determined as ZSM-5 type point through XRD analysis
Son sieve；
(6) by the second filtrate, (main component is Na2CO3, only it is that step (3) are added containing a small amount of Si, Al) part reuse
Sodium carbonate liquor, dilution and filtration and washing for water logging product；The remainder of second filtrate obtains after evaporative crystallization
Na2CO3Solid, reuse to step (1) flyash acid system residue of aluminum-extracted alkaline process roasting in.
The composition of the first filtrate is adjusted in comparative example 4 for synthesizing type ZSM 5 molecular sieve, needs additional silicon source sodium metasilicate
(Mout=201.3g), type ZSM 5 molecular sieve as a result can only be produced, and lead to the primary consumption of flyash acid system residue of aluminum-extracted
Efficiency μ is only 17.16%.And the second obtained filtrate also can not further be prepared as silicon source or silicon source 4A type or other
What types of molecules sieve；I.e. products obtained therefrom only has type ZSM 5 molecular sieve one kind.
From above-described embodiment as can be seen that method provided by the invention can not need additionally to add silicon source or silicon source
Under the conditions of, realize making full use of for flyash acid system residue of aluminum-extracted.It, can while efficiently consumption flyash acid system residue of aluminum-extracted
To produce the 4A type molecular sieve and type ZSM 5 molecular sieve that obtain high added value simultaneously.
In addition, method provided by the invention can also realize making full use of for flyash, without additional addition silicon source or aluminium
Realize flyash conversion production aluminium oxide, 4A type molecular sieve and type ZSM 5 molecular sieve in source.
Claims (14)
1. a kind of method that flyash acid system residue of aluminum-extracted prepares 4A type molecular sieve and type ZSM 5 molecular sieve, including：
(1) flyash acid system residue of aluminum-extracted is subjected to alkaline process roasting, obtains roasting slag charge；The roasting slag charge successively carries out high temperature
Water logging and heat preservation filtering, obtain the first filtrate；
Wherein, the process of the high temperature water logging includes：Progress water logging is mixed with water after the roasting slag charge is removed iron, obtains water
Soak product；Relative to the roasting slag charge of 100g, the dosage of water is 150~200mL；
It is described heat preservation filtering process include：The water logging product is diluted with second filtrate of part, filter and
It rinses, obtains the first filter residue and first filtrate；The main component of second filtrate is sodium carbonate；
(2) first filtrate is subjected to 4A type zeolite-water thermal crystallisation, obtains 4A type molecular sieve and molecular sieve filtrate；Described
The molal weight ratio of the chemical composition of one filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=(10~25):1:(13~20):
(3.5~11):(340~430)；
(3) the molecular sieve filtrate is subjected to type ZSM 5 molecular sieve hydrothermal crystallizing, obtains type ZSM 5 molecular sieve and the second filtrate；
The molal weight ratio of chemical composition in the molecular sieve filtrate is SiO2:Al2O3:Na2O:CO3 2-:H2O=(35~45):1:
(80~90):(75~105):(2100~2300)；
This method does not need additionally to add silicon source or silicon source.
2. according to the method described in claim 1, wherein, in step (1), the process of the alkaline process roasting includes：By 100 weights
The containing sodium carbonate material of the flyash acid system residue of aluminum-extracted and 100~130 parts by weight of measuring part carries out mixed grinding, obtains
Grinding product is crushed to 200 mesh hereinafter, obtaining the fired slags after roasting 60min~120min at 830 DEG C~890 DEG C again
Material.
3. according to the method described in claim 1, wherein, during the high temperature water logging, water soaking temperature is 95 DEG C~105
DEG C, the water logging time is 15min~20min.
4. according to the method described in claim 1, wherein, during the heat preservation filtering, filtration temperature be maintained at 60 DEG C~
80℃。
5. according to the method described in claim 1, wherein, during the heat preservation filtering, the roasting relative to 100g
Slag charge, the dosage of second filtrate are 250~350mL.
6. according to the method described in claim 1, wherein, SiO in first filtrate2With Al2O3Molar ratio be (10~
25)：1.
7. according to the method described in claim 1, wherein, this method further comprises：By first filter residue after drying
Reuse to step (1) is added in the flyash acid system residue of aluminum-extracted.
8. according to the method described in claim 1, wherein, in step (2), the process packet of the 4A type zeolite-water thermal crystallisation
It includes：
A) add water to be hydrolyzed first filtrate, obtain hydrolysate；The additional amount of water meets relative to described in 100g
Slag charge is roasted, the total volume of the hydrolysate is 850~1000mL；
B) CO is passed through into the hydrolysate2Carbon point is carried out, the pH 12~14 of the hydrolysate is made；
C) 4A type molecular sieve seed is added or be added without in the product obtained to step b), is then carried out at 90 DEG C~110 DEG C
15~30h of hydrothermal crystallizing obtains 4A type molecular sieve water heat crystallization product；The dosage of the 4A type molecular sieve seed is the roasting
0~10 weight % of slag charge；
D) the 4A type molecular sieve water heat crystallization product is filtered, obtains the second filter residue and the molecular sieve filtrate；It is described
Second filter residue is dried to obtain the 4A type molecular sieve.
9. according to the method described in claim 1, wherein, SiO in the molecular sieve filtrate2With Al2O3Molar ratio be (35~
45)：1.
10. according to the method described in claim 1, wherein, in step (3), the mistake of the type ZSM 5 molecular sieve hydrothermal crystallizing
Journey includes：
I) organic formwork agent and/or type ZSM 5 molecular sieve crystal seed are added into the molecular sieve filtrate, obtains Synthesis liquid；
Ii) CO is passed through into the Synthesis liquid2Carbon point is carried out, the pH 9~12 of the Synthesis liquid is made；
Iii) product for obtaining step ii) carries out 15~48h of hydrothermal crystallizing at 150 DEG C~190 DEG C, obtains ZSM-5 type point
Son sieve hydrothermal crystallizing product；
Iv) the type ZSM 5 molecular sieve hydrothermal crystallizing product is filtered, obtains third filter residue and second filtrate；Institute
Third filter residue is stated to be washed, dried and roasting obtains the type ZSM 5 molecular sieve.
11. according to the method described in claim 10, wherein, the additional amount of the organic formwork is SiO in the Synthesis liquid23
~10mol%；The organic formwork in tetrapropylammonium hydroxide, 4-propyl bromide, n-propylamine and n-butylamine at least
It is a kind of.
12. according to the method described in claim 10, wherein, the additional amount of the type ZSM 5 molecular sieve crystal seed is the synthesis
SiO in liquid23~15mol%；The SiO of the type ZSM 5 molecular sieve crystal seed2With Al2O3Molar ratio be (50~400)：1.
13. according to the method described in claim 1, wherein, this method further comprises：
During the heat preservation of a part of reuse of second filtrate to step (1) is filtered；By second filtrate
Another part be evaporated after crystallization obtains sodium carbonate, during the alkaline process roasting of reuse to step (1).
14. a kind of utilization method of flyash, this method include：Flyash progress acid system is mentioned aluminium and obtains flyash acid system and mentions aluminium
Residue and aluminium oxide；Flyash acid system residue of aluminum-extracted is prepared by method described in any one of claim 1-13
4A type molecular sieve and type ZSM 5 molecular sieve.
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