CN104341106B - A kind of glass batch and preparation method thereof and a kind of glass and preparation method thereof - Google Patents
A kind of glass batch and preparation method thereof and a kind of glass and preparation method thereof Download PDFInfo
- Publication number
- CN104341106B CN104341106B CN201310325471.5A CN201310325471A CN104341106B CN 104341106 B CN104341106 B CN 104341106B CN 201310325471 A CN201310325471 A CN 201310325471A CN 104341106 B CN104341106 B CN 104341106B
- Authority
- CN
- China
- Prior art keywords
- glass
- acid system
- oxide
- precipitation
- presoma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011521 glass Substances 0.000 title claims abstract description 140
- 239000006066 glass batch Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 93
- 238000000034 method Methods 0.000 claims abstract description 74
- 239000000292 calcium oxide Substances 0.000 claims abstract description 46
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 46
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 45
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 37
- 238000002386 leaching Methods 0.000 claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 35
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 33
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 32
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000003916 acid precipitation Methods 0.000 claims abstract description 31
- 239000010881 fly ash Substances 0.000 claims abstract description 30
- 239000004411 aluminium Substances 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 92
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 80
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000000377 silicon dioxide Substances 0.000 claims description 45
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 40
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 38
- 238000001556 precipitation Methods 0.000 claims description 33
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 27
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 26
- 239000000395 magnesium oxide Substances 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 21
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 19
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 12
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 12
- 238000009993 causticizing Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 238000007885 magnetic separation Methods 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 210000000481 breast Anatomy 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 46
- 239000002956 ash Substances 0.000 abstract description 6
- 239000002910 solid waste Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 229960004424 carbon dioxide Drugs 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 229910052593 corundum Inorganic materials 0.000 description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 description 11
- 238000000137 annealing Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 238000007493 shaping process Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 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 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000010309 melting process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012958 reprocessing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000006124 Pilkington process Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006025 fining agent Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000003605 opacifier Substances 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- NCXOIRPOXSUZHL-UHFFFAOYSA-N [Si].[Ca].[Na] Chemical compound [Si].[Ca].[Na] NCXOIRPOXSUZHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- -1 wherein Chemical compound 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B1/00—Preparing the batches
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of preparation method of glass batch, this method includes：（1）Flyash progress acid system is carried to the acid system residue obtained after aluminium and removes residual acid；（2）Leached with aqueous slkali, separation of solid and liquid obtains leaching liquid and leach residue；（3）Carbon dioxide is passed through into leaching liquid and carries out carbonation decomposition, then separation of solid and liquid obtains silicic acid precipitation and carbonate solution；（4）By step（3）Obtained silicic acid precipitation is mixed with calcium oxide and/or calcium oxide presoma, and is optionally mixed with sodium oxide molybdena and/or sodium oxide molybdena presoma, obtains glass batch.The invention also discloses the preparation method and the glass of preparation of the glass batch prepared by method as described above, and glass.Iron oxide content is extremely low in the glass of the present invention, it is seen that light transmission rate is high, can reach ultra-clear glasses standard, flyash acid system can be greatly improved and puies forward aluminium overall economy quality, and can reduce acid system carries aluminum i ndustry solid waste, realizes Ash Utilization and environment-friendly application.
Description
Technical field
The glass batch prepared the present invention relates to a kind of preparation method of glass batch and by this method, the present invention is also
It is related to the method that glass is prepared by the glass batch, and the glass prepared by this method.
Background technology
Flyash, as the inevitable outcome of coal-fired power plant, is the single industrial solid castoff of Largest In China.Flyash
The recycling for carrying aluminium is not only a big contribution to environmental protection, meanwhile, when China alum clay resource will exhaust,
Also there is important strategic importance.
Aluminum-extracted pulverized fuel ash technique mainly divides acid system, alkaline process, acid and alkali combination method, and ammonium sulfate method etc..In general, acid system
The industrial solid wastes discharge for carrying aluminium is less, and the industrial solid wastes discharge that alkaline process carries aluminium is more.But flyash acid system carries aluminium
Equally exist and carry the problem of aluminium by-product is few, added value is low, significantly impact the economy of this technology.Therefore, flyash is improved
The added value that acid system carries aluminium turns into the focus of research.
Flyash acid system carries the residue of aluminium, according to raw material and technique, dioxide-containing silica typically 50-60 weight % with
On, even up to more than 80-95 weight %.Under concentrated acid effect, the structure of flyash acid system residue of aluminum-extracted is destroyed, shape
Into a large amount of holes, activity is improved.This lays a good foundation for the recycling of flyash acid system residue of aluminum-extracted.Although to powder
Coal ash acid system carries aluminium and has carried out some researchs, but only has the by-products such as white carbon, silicon powder, silica gel, cement and flocculant at present
Product, the exploitation of byproduct is also to be strengthened, further to improve the added value that flyash acid system carries aluminium.
The content of the invention
The invention aims to further improve flyash acid system to put forward the added value of aluminium there is provided a kind of glass batch
Preparation method and preparation glass batch, and the method for glass and the glass of preparation are prepared by the glass batch.
The present inventor is had found under study for action, and flyash acid system residue of aluminum-extracted is removed after residual acid, alkali soluble immersion is used
Take, SiO in the leaching liquid that may be such that2/Al2O3Weight ratio be more than 6, in leaching liquid being passed through carbon dioxide is carbonated
Decompose, obtain silicic acid precipitation and carbonate solution, by silicic acid precipitation according to being actually needed and calcium oxide and/or calcium oxide presoma
Mixing, and optionally mixed with sodium oxide molybdena and/or sodium oxide molybdena presoma, glass batch is can obtain, then, glass batch is appointed
In choosing and potassium oxide, potassium oxide presoma, aluminum oxide, alumina precursor, magnesia, magnesia presoma and glass agent
At least one mixing, gained mixture can be used for the iron oxide content prepared in glass, and the glass prepared extremely low, it is seen that light is saturating
Cross rate high, can reach ultra-clear glasses standard.Especially when the concentration of aqueous slkali is 10-80 weight %, preferably 15-60 weight %, with institute
The silica meter in acid system residue is stated, the mol ratio of the acid system residue and alkali is 1：1-10, preferably 1：2-6；The leaching
Condition include：Temperature is 50-150 DEG C, and preferably 70-130 DEG C, the time is 0.25-6h, in the case of preferably 0.5-3h,
SiO in leaching liquid2/Al2O3Weight ratio can be 30-150, obtained glass batch is more suitable for preparing glass, and can be further
The iron oxide content in glass is reduced, the visible light transmissivity of glass is improved；And technical process is easy under the optimum condition
Realize, with higher economy.Therefore, flyash acid system proposed by the present invention, which carries aluminium by-product glass, can be greatly improved flyash
Acid system puies forward the overall economy quality of aluminium, and reduces the industrial solid wastes that acid system carries aluminium, realizes Ash Utilization and environment-friendly
Using.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of preparation method of glass batch, institute
The method of stating includes：
（1）Flyash progress acid system is carried to the acid system residue obtained after aluminium and removes residual acid；
（2）Leached with aqueous slkali, separation of solid and liquid obtains leaching liquid and leach residue；
（3）Carbon dioxide is passed through into leaching liquid and carries out carbonation decomposition, then separation of solid and liquid obtains silicic acid precipitation and carbon
Acid salt solution；
（4）By step（3）Obtain silicic acid precipitation mixed with calcium oxide and/or calcium oxide presoma, and optionally with oxidation
Sodium and/or the mixing of sodium oxide molybdena presoma, obtain glass batch.
Preferably, the aqueous slkali is the aqueous solution of sodium hydroxide and/or potassium hydroxide.
Preferably, step（2）In, the concentration of aqueous slkali is 10-80 weight %, with the silica in the acid system residue
Meter, the mol ratio of the acid system residue and alkali is 1：1-10；The condition of the leaching includes：Temperature is 50-150 DEG C, and the time is
0.25-6h。
It is further preferred that step（2）In, the concentration of aqueous slkali is 15-60 weight %, with two in the acid system residue
Silica meter, the mol ratio of the acid system residue and alkali is 1：2-6；The condition of the leaching includes：Temperature is 70-130 DEG C, when
Between be 0.5-3h.
Preferably, methods described is also included to step（3）Milk of lime progress causticization is added in obtained carbonate solution anti-
Should, separation of solid and liquid obtains precipitation of calcium carbonate and aqueous slkali；It regard part calcium carbonate precipitation as step（4）In calcium oxide forerunner
Body, step is back to by aqueous slkali（2）In；It is highly preferred that methods described also includes remaining precipitation of calcium carbonate being calcined, stone is prepared
Grey breast, is back to the causticizing reaction；It is further preferred that methods described also includes that precipitation of calcium carbonate is obtained two will be calcined
Carbonoxide is back to step（3）.
Preferably, methods described step（3）In need not to silicic acid precipitation carry out cyclic washing, so as to silicic acid precipitation in meeting
Carry sodium carbonate, potassium carbonate and/or aluminium hydroxide secretly.
Preferably, methods described step（4）In, silicic acid precipitation, calcium oxide and/or calcium oxide presoma, sodium oxide molybdena and/or
The consumption of sodium oxide molybdena presoma makes the weight ratio of silica, sodium oxide molybdena and calcium oxide in obtained glass batch be 68-82：
12-22：6-16.
It is further preferred that methods described also includes：In step（1）Acid system is carried before aluminium, and iron removal by magnetic separation is carried out to flyash.
Second aspect, the invention provides a kind of glass batch prepared by method as described above.
The third aspect, the invention provides a kind of preparation method of glass, methods described includes：
（1）By glass batch optionally with potassium oxide, potassium oxide presoma, aluminum oxide, alumina precursor, magnesia,
At least one of magnesia presoma and glass agent are mixed, wherein, the glass batch is that glass as described above is matched somebody with somebody
Close material；
（2）By step（1）Obtained mixture is founded, is molded and annealed.
Fourth aspect, the invention provides a kind of glass prepared by method as described above.
The inventive method prepare glass batch, optionally with before potassium oxide, potassium oxide presoma, aluminum oxide, aluminum oxide
Drive the mixing of at least one of body, magnesia, magnesia presoma and glass agent, you can for preparing glass.Institute of the present invention
Iron oxide content is extremely low in the glass of preparation, it is seen that light transmission rate is high, can reach ultra-clear glasses standard, flyash can be greatly improved
Acid system puies forward aluminium overall economy quality, and can reduce acid system and carry aluminum i ndustry solid waste, realize Ash Utilization and it is environment-friendly should
With.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
On the one hand, the invention provides a kind of preparation method of glass batch, this method includes：
（1）Flyash progress acid system is carried to the acid system residue obtained after aluminium and removes residual acid；
（2）Leached with aqueous slkali, separation of solid and liquid obtains leaching liquid and leach residue；
（3）Carbon dioxide is passed through into leaching liquid and carries out carbonation decomposition, then separation of solid and liquid obtains silicic acid precipitation and carbon
Acid salt solution；
（4）By step（3）Obtain silicic acid precipitation mixed with calcium oxide and/or calcium oxide presoma, and optionally with oxidation
Sodium and/or the mixing of sodium oxide molybdena presoma, obtain glass batch.
In the present invention, glass batch refers to that sodium calcium silicon ratio meets the glass batch of glass composition.
In the present invention, aqueous slkali is preferably the aqueous solution of sodium hydroxide and/or potassium hydroxide.
According to the present invention, glass batch is prepared while in accordance with the above method, you can realize the purpose of the present invention, that is, obtain
Leaching liquid in SiO2/Al2O3Weight ratio be more than 6, obtained glass batch is suitable to prepare iron oxide in glass, glass
Content is extremely low, it is seen that light transmission rate is high, can reach ultra-clear glasses standard.But under preferable case, step（2）In, aqueous slkali it is dense
Spend for 10-80 weight %, in terms of the silica in the acid system residue, the mol ratio of the acid system residue and alkali is 1：1-10；
The condition of leaching includes：Temperature is 50-150 DEG C, and the time is 0.25-6h.In the case of further preferably, step（2）In, aqueous slkali
Concentration be 15-60 weight %, in terms of the silica in the acid system residue, the mol ratio of the acid system residue and alkali is 1：
2-6；The condition of leaching includes：Temperature is 70-130 DEG C, and the time is 0.5-3h.Under above-mentioned preferable case, SiO in leaching liquid2/
Al2O3Weight ratio up to 30-150, obtained glass batch is more suitable for preparing glass, and further can reduce in glass
Iron oxide content, further improves the visible light transmissivity of glass.Also, under above-mentioned preferable case, technical process is easier to
Realize, with more preferable economy.
In the present invention, leaching is generally carried out under agitation.
In the present invention, the method for aluminium is put forward without particular/special requirement for flyash acid system, can be using commonly used in the art various
Method, for example, CN102153117A, CN1927716A, CN101811712A, CN101844783A, CN101870489A,
Aluminum-extracted pulverized fuel ash method disclosed in CN102101686A, CN102020299A, CN102020300A, CN101254933A, this
The content of a little patent applications is incorporated herein by way of full text is introduced, and will not be repeated here.
In the present invention, in order to further reduce influence of the iron to glass quality, the inventive method is preferably also included in step
（1）Flyash acid system carries the step of carrying out iron removal by magnetic separation to flyash before aluminium.
In the present invention, for acid system residue without particular/special requirement, the acquisition of aluminium method can be proposed for acid system commonly used in the art
Acid system residue obtained by acid system residue, each method as disclosed above, generally, silica contains in acid system residue
Measure as 50-95 weight %, the content of aluminum oxide is 0.5-50 weight %.
Because the content of silica in acid system residue is 50-95 weight %, through step（2）After leaching, silica will be several
All it is dissolved in aqueous slkali, therefore, the leach residue obtained after leaching has been greatly reduced relative to the amount of acid system residue, leaching
Take residue according to its composition and property, can be discharged directly as industrial solid castoff or further be subject to profit as the raw material of industry
With.
Step of the present invention（1）In, for removing in flyash acid system residue of aluminum-extracted, residual sour method is without particular/special requirement, for example
Methods described can include acid system residue being calcined 15-300min at 200-1000 DEG C, be calcined preferably at 300-850 DEG C
30-180min, and/or cleaned with water to neutrality.In order to preferably remove under residual acid, preferable case, residual sour method bag is removed
Include acid system residue being calcined after 15-300min at 200-1000 DEG C and cleaned again with water to neutrality.In the case of more preferably, remove residual
The method of acid includes acid system residue being calcined after 30-180min at 300-850 DEG C being cleaned to neutrality with water again.
Step of the present invention（3）In, in order that carbonation decomposition carries out more thorough, even if silicic acid precipitates more complete, carbonic acid
Change decomposing terminal pH value of solution and be preferably shorter than 11, more preferably less than 9, be still more preferably 8-9.
Step of the present invention（3）In, for carbon dioxide source without particular/special requirement, for example, can be by being calcined calcium carbonate
Precipitation is obtained, can also outsourcing acquisition or the acquisition of kiln burning waste gas.It will be understood by those skilled in the art that for carbonic acid
The volumetric concentration for changing the carbon dioxide in the gas decomposed should be greater than 10%, optimal with 40% or so, the carbon dioxide and kiln of outsourcing
The impurity for the carbon dioxide that stove burning waste gas is obtained should not influence carbonation decomposition process.
Step of the present invention（3）In, it can carry sodium carbonate and/or potassium carbonate and a small amount of aluminium hydroxide secretly in silicic acid precipitation, and
Sodium oxide molybdena, potassium oxide and aluminum oxide are also the important composition of glass batch.Therefore, step（3）In silicic acid need not be precipitated
Carry out cyclic washing.
In order to further reduce cost, the inventive method preferably also includes to step（3）Add in obtained carbonate solution
Enter milk of lime and carry out causticizing reaction, separation of solid and liquid obtains precipitation of calcium carbonate and aqueous slkali；It regard part calcium carbonate precipitation as step
（4）In calcium oxide presoma, aqueous slkali is back to step（2）In.
In causticizing reaction of the present invention, in terms of calcium oxide, the mol ratio of carbonate and milk of lime is preferably 1：0.9-1.1；It is severe
The temperature of change is preferably 70-95 DEG C, and the time is preferably 0.5-3h.
In the present invention, aqueous slkali is back to step（2）In, it will be understood by those skilled in the art that because of step（3）
Silicic acid precipitation entrainment carbonate and causticizing reaction obtain precipitation of calcium carbonate entrainment alkali, the loss of a small amount of alkali will be caused, because
This can supplement appropriate alkali as needed in the aqueous slkali that causticizing reaction is obtained and be back to step（2）In to meet step（2）
In to alkali the need for.
In the present invention, part calcium carbonate precipitation is regard as step（4）In calcium oxide presoma, precipitation of calcium carbonate entrainment
Alkali, and sodium oxide molybdena and potassium oxide are also the important composition of glass batch.It therefore, there is no need to wash precipitation of calcium carbonate repeatedly
Wash to prepare purity calcium carbonate, part calcium carbonate precipitation can be directly used as step（4）In calcium oxide presoma.
In glass, the weight ratio of silica and sodium oxide molybdena and calcium oxide is generally 68-82：12-22：6-16, therefore,
In step of the present invention（4）In, silicic acid precipitation is mixed with calcium oxide and/or calcium oxide presoma according to being actually needed, and optionally
Mixed with sodium oxide molybdena and/or sodium oxide molybdena presoma, can obtain glass batch, wherein, silicic acid precipitation, calcium oxide and/or oxidation
The consumption of calcium presoma, sodium oxide molybdena and/or sodium oxide molybdena presoma makes silica, sodium oxide molybdena and oxygen in obtained glass batch
The weight ratio for changing calcium is 68-82：12-22：6-16, preferably 69-76：12-16：8-14.
By step（3）The part calcium carbonate precipitation that obtained carbonate solution progress causticizing reaction is obtained is used as before calcium oxide
The aforementioned proportion relation of silico-calcium can be met by driving body.
In step（4）In, by step（3）Obtained silicic acid precipitation is mixed with calcium oxide and/or calcium oxide presoma, and is appointed
Choosing is mixed with sodium oxide molybdena and/or sodium oxide molybdena presoma, obtains glass batch, and the glass batch includes carrying secretly in silicic acid precipitation
Carbonate and aluminium hydroxide, when by step（3）The part calcium carbonate that obtained carbonate solution progress causticizing reaction is obtained sinks
Form sediment when being used as calcium oxide presoma, in addition to the alkali carried secretly in precipitation of calcium carbonate, the glass batch may make up glass composition
90-100 weight %.
In the present invention, sodium oxide molybdena presoma is to refer to that during glass preparation decomposable asymmetric choice net obtains the material of sodium oxide molybdena, example
Such as, can be sodium carbonate, sodium hydroxide etc.；Calcium oxide presoma is to refer to that decomposable asymmetric choice net obtains calcium oxide during glass preparation
Material, for example, can be for calcium carbonate, calcium hydroxide etc..
In the present invention, because the part calcium carbonate only obtained with causticizing reaction is precipitated as calcium oxide presoma, in order to
Cost is further reduced, the inventive method preferably also includes remaining precipitation of calcium carbonate being calcined, generation calcium oxide and carbon dioxide,
Calcium oxide can be configured to milk of lime, be back to causticizing reaction, and carbon dioxide can be back to step（3）.It is remaining in the present invention
Precipitation of calcium carbonate is for as the part calcium carbonate of calcium oxide presoma precipitation, i.e. the amount of remaining precipitation of calcium carbonate
The total amount of the precipitation of calcium carbonate obtained with the amount sum of the part calcium carbonate precipitation as calcium oxide presoma for causticizing reaction.
Second aspect, present invention also offers glass batch prepared by method as described above.
The third aspect, the invention provides a kind of preparation method of glass, this method includes：
（1）By glass batch optionally with potassium oxide, potassium oxide presoma, aluminum oxide, alumina precursor, magnesia,
At least one of magnesia presoma and glass agent are mixed, wherein, glass batch is glass batch as described above；
（2）By step（1）Obtained mixture is founded, is molded and annealed.
As described above, the glass batch of the present invention may make up the 90-100 weight % of glass composition.Glass batch is appointed
In choosing and potassium oxide, potassium oxide presoma, aluminum oxide, alumina precursor, magnesia, magnesia presoma and glass agent
At least one is mixed, you can directly to be founded, be molded and be annealed the glass batch of the present invention, now glass batch
Constitute 100 weight % of glass composition.That is step（1）Obtained mixture can also may be used for glass batch of the invention in itself
Think the glass batch and potassium oxide, potassium oxide presoma, aluminum oxide, alumina precursor, magnesia, magnesia of the present invention
The mixture that at least one of presoma and glass agent are mixed to get.
The composition of glass is generally comprised：12-22 weight % sodium oxide molybdena, 6-16 weight % calcium oxide and 68-82 weight %'s
Silica；Preferably include：12-16 weight % sodium oxide molybdena, 8-14 weight % calcium oxide and 69-76 weight % silica.
Sodium oxide molybdena and calcium oxide can partly be replaced by potassium oxide and magnesia, help to improve glass function and processing characteristics.Therefore, root
The need for according to glass function and processing characteristics, can optionally with potassium oxide, potassium oxide presoma, aluminum oxide, alumina precursor, oxygen
Change the mixing of at least one of magnesium, magnesia presoma and glass agent.
In the present invention, potassium oxide presoma is to refer to that during glass preparation decomposable asymmetric choice net obtains the material of potassium oxide, oxygen
It is to refer to that during glass preparation decomposable asymmetric choice net obtains the material of aluminum oxide to change aluminium presoma, and magnesia presoma is to refer in glass
Decomposable asymmetric choice net obtains the material of magnesia in glass preparation process, for example, potassium oxide presoma, alumina precursor and magnesia forerunner
Body can be respectively carbonate, nitrate or sulfate of potassium, aluminium and magnesium etc..
In the present invention, glass agent can use glass manufacture in commonly use glass agent, for example can selected from fining agent,
One or more in Oxidizing and Reducing Agents, colouring agent, decolorising agent, opacifiers and cosolvent etc..Fining agent for example can be
Arsenic trioxide, antimony oxide, nitrate, sulfate, fluoride, ceria, ammonium salt etc.；Oxidant for example can be nitre
Hydrochlorate, arsenic trioxide, ceria etc.；Reducing agent for example can be carbon, potassium tartrate, glass putty and compound, metallic aluminium powder
With metal antimony powder etc.；Colouring agent is such as can be the compound of transition metal and thulium；Decolorising agent is for example
Can be sodium nitrate, potassium nitrate, antimony oxide, cerium oxide, manganese oxide etc.；Opacifiers for example can for fluoride, phosphate,
Sulfate and chloride etc.；Cosolvent is such as can be fluoride, boride, barium compound and nitrate.As described above, same
A variety of auxiliary agents, such as nitrate and sulfate can be played a part of sometimes in glass melting process by planting compound.Meanwhile, institute
Stating usage amount of different types of single auxiliary agent in glass melting process can change in very large range, for example, can be
0.01-7 weight %.
In the present invention, potassium oxide, potassium oxide presoma, aluminum oxide, alumina precursor, magnesia, magnesia presoma
With the consumption of glass agent, can be according to the concrete content of each component in the glass batch of the present invention, and glass technology
Condition and purposes and accordingly adjust, this is known to those skilled in the art, will not be repeated here.
, can be using the conventional method in this area for specific preparation technology without particular/special requirement in the present invention.It is general to carry out
After founding, be molded and annealing, it can as needed be reprocessed, obtain glass product.
In the present invention, the method for founding, being molded, anneal and reprocess can use ability without particular/special requirement
The common process method in domain.For example, melting process can be carried out by following technique：It is heated to after all raw materials are well mixed
800-1000 DEG C, generate silicate；Obtained silicate is heated to 1200-1300 DEG C, glass metal is formed；By obtained glass
Liquid is heated to 1400-1500 DEG C, carries out the clarification of glass metal；At a temperature of less than 100-200 DEG C of glass metal clarifying temp, enter
The homogenizing of row glass metal；1000-1300 DEG C of cooling is cooled to after homogenizing, glass metal is possessed the viscosity needed for shaping.
But, it will be understood by those skilled in the art that each stage of glass smelting connect each other and influence,
In actual melting process, the above stage is often while progress or staggeredly progress, depend primarily on the process system founded
The characteristics of with glass melter structure.
Glass shaping can be using the various techniques commonly used in production, such as pressing, blowing method, drawing shaping, calendering
Shaping, moulding by casting, float glass process shaping etc..For the production of sodium calcium plate glass, preferably float glass process shaping and calendering formation.
Meanwhile, it is too fast and cause to burst in order to avoid cooling down, one should be also incubated at an annealing temperature as glass shaping is latter
The section time, then cooled to according to chilling temperature system after certain temperature and stop heating, allow it to slowly cool to 100 naturally with stove
Below DEG C, come out of the stove, room temperature is cooled in atmosphere.If glass must anneal again after annealing through stress disqualified upon inspection, to prevent
Burst during processing.
Glass after shaping, which only has minority, can meet user's request, and the overwhelming majority needs to be reprocessed, and can just be accorded with
Close desired glassware.The reprocessing of glass generally can be divided into cold working（Cutting, grinding, polishing etc.）, hot-working and surface
Handle three major types.In addition, glass reprocessing also includes sealing-in and the intensive treatment of glass（It is physical toughened and chemical enhanced）Deng.
The reprocessing technique being well known to the skilled person above, will not be repeated here.
Fourth aspect, present invention also offers glass prepared by method as described above.
Embodiment
The present invention is further illustrated for following embodiment, but and is not so limited the present invention.
In the examples below：
Chemical composition analysis, is carried out according to GBT 1574-2007.
Glass visible light transmissivity is determined, according to IS0 9050：2003 (E) are carried out.
Flyash is derived from the quasi- a certain power plant in Ge Er areas in the Inner Mongol, constitutes as follows：（Weight %）
| SiO2 | Al2O3 | Fe2O3 | FeO | MgO | CaO | Na2O | K2O | H2O | TiO2 | P2O5 | MnO | S | Loss on ignition | Total amount |
| 40.01 | 50.71 | 1.41 | 0.35 | 0.47 | 2.85 | 0.12 | 0.5 | 0.024 | 1.57 | 0.17 | 0.022 | 0.22 | 1.41 | 99.81 |
Embodiment 1
The embodiment is used for the preparation method and the preparation method of glass for illustrating the glass batch of the present invention.
（1）The flyash of composition described above is taken, in sulfuric acid concentration 98%, 260 DEG C of temperature, time 100min, liquid-solid ratio 4：1
Under the conditions of reacted.Afterwards, the aluminum sulfate for generation in unreacted sulfuric acid, filter residue, and absorbed portion sulfuric acid are filtered out.
It is 6 by liquid-solid ratio at 300 DEG C after roasting deacidification：1 adds water dissolution 30min in dry slag, obtains aluminum sulfate solution and acid system is residual
Slag.It is 72.8 weight % to determine dioxide-containing silica in acid system residue, and alumina content is 13 weight %, and iron oxide content is 0.4
Weight %.
（2）Acid system residue is calcined 60min at 800 DEG C, cleaned after cooling with water to neutrality.Then by acid at 95 DEG C
Method residue stirs leaching in 1 hour, in terms of the silica in acid system residue, the acid system in 30 weight % sodium hydroxide solutions
The mol ratio of residue and alkali is 1：3, it is filtrated to get leaching liquid and leach residue.SiO in leaching liquid2/Al2O3Weight ratio be 98,
Silica recovery rate is 91%.
（3）Carbon dioxide is passed through in leaching liquid and carries out carbonation decomposition, stops being passed through carbon dioxide when pH is 8.8.
It is filtrated to get silicic acid precipitation and sodium carbonate liquor.Silicic acid precipitation solid content is 30%, and butt sodium oxide content is 3.5 weight %,
SiO2/Al2O3Weight ratio be 95.
（4）In step（3）Milk of lime is added in obtained sodium carbonate liquor, in terms of calcium oxide, sodium carbonate and milk of lime
Mol ratio is 1：1.1, stirring reaction 1 hour, is filtrated to get precipitation of calcium carbonate and sodium hydroxide solution at 95 DEG C.Calcium carbonate sinks
Shallow lake solid content is 50%, butt Na2O content is 2.8 weight %.
（5）By step（3）Obtained silicic acid precipitation and step（4）Obtained part calcium carbonate precipitation and sodium carbonate is mixed
Close, obtain glass batch, the consumption of part calcium carbonate precipitation and sodium carbonate causes in the glass batch that is obtained after mixing, with
Each oxide meter, constitutes and is：14.5 weight % sodium oxide molybdena, 12.3 weight % calcium oxide, 0.7 weight % aluminum oxide, 72.5 weights
Measure % silica.
（6）Take step（5）Obtained glass batch 300g, the crucible of 300ml capacity is placed in high temperature Muffle furnace, is risen
Temperature is to 1300 DEG C, point 3 addition glass batches.After insulation 15 minutes, 1500 DEG C of glass clarifying temperature is risen to, 2 hours are incubated.
During incubation, with stainless steel bar stirring several times, it is ensured that without heavy seed, make homogenization of glass.Mould is placed on electric furnace
On be preheated to 1000 DEG C, take out one piece of 100mm × 100mm × 5mm of crucible cast molding chunk glass, and be transferred to annealing immediately
With in low temperature Muffle furnace, 30 minutes or so are incubated at 580 DEG C, is annealed.Then 1 DEG C per minute is pressed, is cooled to after 200 DEG C and breaks
Electricity, less than 100 DEG C are slowly cooled to stove, is come out of the stove, room temperature is cooled in atmosphere naturally.Complete annealing.Afterwards, flat board glass
Glass cuts into the shape for being adapted to processing and experiment test, and is ground and polishing.
Determine the visible light transmissivity of the glass of the content of iron oxide and 3mm thickness in gained glass.It the results are shown in Table 1.
Embodiment 2
The embodiment is used for the preparation method and the preparation method of glass for illustrating the glass batch of the present invention.
（1）The flyash of composition described above is taken, 0.7 weight % is down to by iron removal by magnetic separation rear oxidation iron content.Add 37 weights
It is 4.5 to measure % hydrochloric acid and carry out alumina ratio in the molten reaction of acid, hydrochloric acid and flyash：1,200 DEG C of reaction temperature, the reaction time 2 is small
When.Separation of solid and liquid obtains liquor alumini chloridi and acid system residue.It is 91.2 weight %, oxygen to determine dioxide-containing silica in acid system residue
Change aluminium content is 2.1 weight %, and iron oxide content is 0.2 weight %.
（2）Acid system residue is calcined 120min at 500 DEG C, cleaned after cooling with water to neutrality.Then will at 70 DEG C
Acid system residue stirs leaching in 3 hours, in terms of the silica in acid system residue, the acid in 15 weight % sodium hydroxide solutions
The mol ratio of method residue and alkali is 1：2.It is filtrated to get leaching liquid and leach residue.SiO in leaching liquid2/Al2O3Weight ratio is
128, silica recovery rate is 86%.
（3）Carbon dioxide is passed through in leaching liquid and carries out carbonation decomposition, stops being passed through carbon dioxide when pH is 8.5.
It is filtrated to get silicic acid precipitation and sodium carbonate liquor.Silicic acid precipitation solid content is 26%, and butt sodium oxide content is 3.3 weight %,
SiO2/Al2O3Weight ratio be 125.
（4）In step（3）Milk of lime is added in obtained sodium carbonate liquor, in terms of calcium oxide, sodium carbonate and milk of lime
Mol ratio is 1：0.9, stirring reaction 3 hours, are filtrated to get precipitation of calcium carbonate and sodium hydroxide solution at 70 DEG C.Calcium carbonate sinks
Shallow lake solid content is 52%, and butt sodium oxide content is 3.5 weight %.
（5）By step（3）Obtained silicic acid precipitation and step（4）Obtained part calcium carbonate precipitation and sodium carbonate is mixed
Close, obtain glass batch, the consumption of part calcium carbonate precipitation and sodium carbonate causes in the glass batch that is obtained after mixing, with
Each oxide meter, constitutes and is：15.2 weight % sodium oxide molybdena, 14.8 weight % calcium oxide, 0.5 weight % aluminum oxide, 69.5 weights
Measure % silica.
（6）Take step（5）Obtained glass batch 300g, the crucible of 300ml capacity is placed in high temperature Muffle furnace, is risen
Temperature is to 1300 DEG C, point 3 addition glass batches.After insulation 15 minutes, 1500 DEG C of glass clarifying temperature is risen to, 2 hours are incubated.
During incubation, with stainless steel bar stirring several times, it is ensured that without heavy seed, make homogenization of glass.Mould is placed on electric furnace
On be preheated to 1000 DEG C, take out one piece of 100mm × 100mm × 5mm of crucible cast molding chunk glass, and be transferred to annealing immediately
With in low temperature Muffle furnace, 30 minutes or so are incubated at 550 DEG C, is annealed.Then 1 DEG C per minute is pressed, is cooled to after 200 DEG C and breaks
Electricity, less than 100 DEG C are slowly cooled to stove, is come out of the stove, room temperature is cooled in atmosphere naturally.Complete annealing.Afterwards, flat board glass
Glass cuts into the shape for being adapted to processing and experiment test, and is ground and polishing.
Determine the visible light transmissivity of the glass of iron oxide content and 3mm thickness in gained glass.It the results are shown in Table 1.
Embodiment 3
The embodiment is used for the preparation method and the preparation method of glass for illustrating the glass batch of the present invention.
（1）The flyash of composition described above is taken, in sulfuric acid concentration 98%, 210 DEG C of temperature, time 50min, liquid-solid ratio 4：1 bar
Reacted under part.Afterwards, the aluminum sulfate for generation in unreacted sulfuric acid, filter residue, and absorbed portion sulfuric acid are filtered out.
It is 6 by liquid-solid ratio at 300 DEG C after roasting deacidification：1 adds water dissolution 30min in dry slag, obtains aluminum sulfate solution and acid system is residual
Slag.It is 57.8 weight % to determine dioxide-containing silica in acid system residue, and alumina content is 23.5 weight %, and iron oxide content is
0.9 weight %.
（2）Acid system residue is calcined 180min at 300 DEG C, cleaned after cooling with water to neutrality.Then will at 130 DEG C
Acid system residue stirs leaching in 2 hours, in terms of the silica in acid system residue, the acid in 60 weight % sodium hydroxide solutions
The mol ratio of method residue and alkali is 1：6, it is filtrated to get leaching liquid and leach residue.SiO in leaching liquid2/Al2O3Weight ratio be
35, silica recovery rate is 93%.
（3）Carbon dioxide is passed through in leaching liquid and carries out carbonation decomposition, stops being passed through carbon dioxide when pH is 9.Cross
Filter obtains silicic acid precipitation and sodium carbonate liquor.Silicic acid precipitation solid content is 35%, and butt sodium oxide content is 3.9 weight %, SiO2/
Al2O3Weight ratio be 33.
（4）In step（3）Milk of lime is added in obtained sodium carbonate liquor, in terms of calcium oxide, sodium carbonate and milk of lime
Mol ratio is 1：1.0, stirring reaction 2 hours, are filtrated to get precipitation of calcium carbonate and sodium hydroxide solution at 83 DEG C.Calcium carbonate sinks
Shallow lake solid content 50%, butt sodium oxide content is 3.2 weight %.
（5）By step（3）Obtained silicic acid precipitation and step（4）Obtained part calcium carbonate precipitation and sodium carbonate is mixed
Close, obtain glass batch, the consumption of part calcium carbonate precipitation and sodium carbonate causes in the glass batch that is obtained after mixing, with
Following oxide meter, constitutes and is：12.2 weight % sodium oxide molybdena, 8.2 weight % calcium oxide, 2.3 weight % aluminum oxide,
77.3 weight % silica.
（6）Take step（5）Obtained glass batch 300g, the crucible of 300ml capacity is placed in high temperature Muffle furnace, is risen
Temperature is to 1300 DEG C, point 3 addition glass batches.After insulation 15 minutes, 1500 DEG C of glass clarifying temperature is risen to, 2 hours are incubated.
During incubation, with stainless steel bar stirring several times, it is ensured that without heavy seed, make homogenization of glass.Mould is placed on electric furnace
On be preheated to 1000 DEG C, take out one piece of 100mm × 100mm × 5mm of crucible cast molding chunk glass, and be transferred to annealing immediately
With in low temperature Muffle furnace, 30 minutes or so are incubated at 600 DEG C, is annealed.Then 1 DEG C per minute is pressed, is cooled to after 200 DEG C and breaks
Electricity, less than 100 DEG C are slowly cooled to stove, is come out of the stove, room temperature is cooled in atmosphere naturally.Complete annealing.Afterwards, flat board glass
Glass cuts into the shape for being adapted to processing and experiment test, and is ground and polishing.
Determine the visible light transmissivity of the glass of the content of iron oxide and 3mm thickness in gained glass.It the results are shown in Table 1.
Embodiment 4
The embodiment is used for the preparation method and the preparation method of glass for illustrating the glass batch of the present invention.
Method according to embodiment 1 prepares glass batch and glass, unlike, step（2）In, with acid system residue
Silica meter, the mol ratio of the acid system residue and alkali is 1：1.Silica recovery rate is determined, is determined in gained glass
The visible light transmissivity of the content of iron oxide and the glass of 3mm thickness.It the results are shown in Table 1.
Embodiment 5
The embodiment is used for the preparation method and the preparation method of glass for illustrating the glass batch of the present invention.
Method according to embodiment 1 prepares glass batch and glass, unlike, step（2）In, with acid system residue
Silica meter, the mol ratio of the acid system residue and alkali is 1：10.Silica recovery rate is determined, is determined in gained glass
The visible light transmissivity of the content of iron oxide and the glass of 3mm thickness.It the results are shown in Table 1.
Embodiment 6
The embodiment is used for the preparation method and the preparation method of glass for illustrating the glass batch of the present invention.
Method according to embodiment 1 prepares glass batch and glass, unlike, step（2）In, sodium hydroxide solution
Concentration be 10 weight %.Silica recovery rate is determined, the content and the glass of 3mm thickness of iron oxide in gained glass is determined
Visible light transmissivity.It the results are shown in Table 1.
Embodiment 7
The embodiment is used for the preparation method and the preparation method of glass for illustrating the glass batch of the present invention.
Method according to embodiment 1 prepares glass batch and glass, unlike, step（2）In, sodium hydroxide solution
Concentration be 80 weight %.Silica recovery rate is determined, the content and the glass of 3mm thickness of iron oxide in gained glass is determined
Visible light transmissivity.It the results are shown in Table 1.
Embodiment 8
The embodiment is used for the preparation method and the preparation method of glass for illustrating the glass batch of the present invention.
Method according to embodiment 1 prepares glass batch and glass, unlike, step（2）In, by 30 weight %'s
Sodium hydroxide solution replaces with 30 weight % sodium hydroxide and the mixed solution of potassium hydroxide, wherein, sodium hydroxide and hydroxide
The weight ratio of potassium is 2：1.Silica recovery rate is determined, the content and the glass of 3mm thickness of iron oxide in gained glass is determined
Visible light transmissivity.It the results are shown in Table 1.
Table 1
As it can be seen from table 1 in the glass prepared using the inventive method, glass iron oxide content in below 130ppm,
Ultra-clear glasses standard is met and exceeded（Iron oxide content is less than 150ppm）, and the visible light transmissivity of 3mm thickness is 92%
More than, also meet and exceed ultra-clear glasses standard（3mm thickness visible light transmissivity is 91.5%）.
Embodiment 1 is compared with embodiment 4 and 5 as can be seen that with the silica in the acid system residue respectively
Meter, the mol ratio of the acid system residue and alkali is 1：2-6, can further reduce the iron oxide content in obtained glass, enter one
Step improves the visible light transmissivity of glass, and processing range is easier to realize, silica recovery rate is higher, good economy performance；Will
Embodiment 1 is compared with embodiment 6 and 7 respectively can be seen that the concentration of aqueous slkali for 15-60 weight %, can further reduce
Iron oxide content in glass, further improves the visible light transmissivity of glass, and processing range is easier to realize, silica is carried
Take rate higher, good economy performance.
The inventive method prepare glass batch, optionally with before potassium oxide, potassium oxide presoma, aluminum oxide, aluminum oxide
Drive the mixing of at least one of body, magnesia, magnesia presoma and glass agent, you can for preparing glass.Institute of the present invention
Iron oxide content is extremely low in the glass of preparation, it is seen that light transmission rate is high, can reach ultra-clear glasses standard, flyash can be greatly improved
Acid system puies forward aluminium overall economy quality, and can reduce acid system and carry aluminum i ndustry solid waste, realize Ash Utilization and it is environment-friendly should
With.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (7)
1. a kind of preparation method of ultra-clear glasses batch, it is characterised in that methods described includes：
(1) flyash progress acid system is carried to the acid system residue obtained after aluminium and removes residual acid；
(2) leached with aqueous slkali, separation of solid and liquid obtains leaching liquid and leach residue；
(3) carbon dioxide is passed through into leaching liquid and carries out carbonation decomposition, then separation of solid and liquid obtains silicic acid precipitation and carbonate
Solution；
(4) the silicic acid precipitation obtained step (3) is mixed with calcium oxide and/or calcium oxide presoma, and optionally with sodium oxide molybdena and/
Or the mixing of sodium oxide molybdena presoma, obtain glass batch；
Cyclic washing need not be carried out to silicic acid precipitation in step (3), so as to which sodium carbonate, potassium carbonate can be carried secretly in silicic acid precipitation
And/or aluminium hydroxide；
Before step (1) acid system carries aluminium, iron removal by magnetic separation is carried out to flyash；
The content of silica is 50-95 weight % in the acid system residue that step (1) is obtained, and the content of aluminum oxide is 0.5-50 weights
% is measured, acid system residue, which removes residual sour method, to be included：Acid system residue is calcined 15-300min at 200-1000 DEG C, and/or used
Water is cleaned to neutrality；
In step (2), the concentration of aqueous slkali is 10-80 weight %, in terms of the silica in the acid system residue, the acid system
The mol ratio of residue and alkali is 1：1-10；The condition of the leaching includes：Temperature is 50-150 DEG C, and the time is 0.25-6h；
Methods described also includes：Milk of lime is added in the carbonate solution obtained to step (3) and carries out causticizing reaction, separation of solid and liquid
Obtain precipitation of calcium carbonate and aqueous slkali；Using part calcium carbonate precipitation as the calcium oxide presoma in step (4), aqueous slkali is returned
For in step (2).
2. according to the method described in claim 1, wherein, the aqueous slkali is the aqueous solution of sodium hydroxide and/or potassium hydroxide.
3. according to the method described in claim 1, wherein, in step (2), the concentration of aqueous slkali is 15-60 weight %, with described
Silica meter in acid system residue, the mol ratio of the acid system residue and alkali is 1：2-6；The condition of the leaching includes：Temperature
Spend for 70-130 DEG C, the time is 0.5-3h.
4. according to the method described in claim 1, wherein, methods described also includes：Remaining precipitation of calcium carbonate is calcined, stone is prepared
Grey breast, is back to the causticizing reaction.
5. method according to claim 4, wherein, methods described also includes：The dioxy that precipitation of calcium carbonate is obtained will be calcined
Change carbon and be back to step (3).
6. the method according to any one of claim 1-5, wherein, in step (4), silicic acid precipitation, calcium oxide and/or oxygen
Change the consumption of calcium presoma, sodium oxide molybdena and/or sodium oxide molybdena presoma make silica in obtained glass batch, sodium oxide molybdena and
The weight ratio of calcium oxide is 68-82：12-22：6-16.
7. a kind of preparation method of ultra-clear glasses, it is characterised in that methods described includes：
(1) method according to any one in claim 1-6 prepares glass batch, by the glass batch optionally with
In potassium oxide, potassium oxide presoma, aluminum oxide, alumina precursor, magnesia, magnesia presoma and glass agent at least
One kind mixing；
(2) mixture for obtaining step (1) is founded, is molded and annealed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310325471.5A CN104341106B (en) | 2013-07-30 | 2013-07-30 | A kind of glass batch and preparation method thereof and a kind of glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310325471.5A CN104341106B (en) | 2013-07-30 | 2013-07-30 | A kind of glass batch and preparation method thereof and a kind of glass and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104341106A CN104341106A (en) | 2015-02-11 |
| CN104341106B true CN104341106B (en) | 2017-08-04 |
Family
ID=52497641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310325471.5A Active CN104341106B (en) | 2013-07-30 | 2013-07-30 | A kind of glass batch and preparation method thereof and a kind of glass and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104341106B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112624609A (en) * | 2020-12-30 | 2021-04-09 | 上海神网辐射防护器材有限公司 | Production process of anti-radiation glass |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759210A (en) * | 2010-01-18 | 2010-06-30 | 马昱昭 | Method for extracting high purity alumina and silica gel from coal ash |
| CN101966999A (en) * | 2010-11-11 | 2011-02-09 | 中国地质大学（北京） | Method for extracting aluminum oxide and white carbon black through two-step alkaline leaching method by adopting high-alumina fly ash |
-
2013
- 2013-07-30 CN CN201310325471.5A patent/CN104341106B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759210A (en) * | 2010-01-18 | 2010-06-30 | 马昱昭 | Method for extracting high purity alumina and silica gel from coal ash |
| CN101966999A (en) * | 2010-11-11 | 2011-02-09 | 中国地质大学（北京） | Method for extracting aluminum oxide and white carbon black through two-step alkaline leaching method by adopting high-alumina fly ash |
Non-Patent Citations (1)
| Title |
|---|
| 粉煤灰提铝渣中二氧化硅在高浓度碱液中的溶解行为;吴艳等;《中国有色金属学报》;20080630;第18卷;正文摘要，第一节实验部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104341106A (en) | 2015-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9517965B2 (en) | Method for preparing a soda-lime-silica glass basic formulation and a method for extracting aluminum from coal ash for co-production of glass | |
| CN101857355B (en) | Method for producing glass beads used for curing high-level nuclear wastes | |
| CN109052969B (en) | Method for producing microcrystalline glass by using calcium iron garnet type red mud | |
| CN107417122B (en) | A method of comprehensive utilization vanadium extraction residues prepare devitrified glass | |
| CN100383071C (en) | Sludge microcrystalline glass and its preparation method | |
| CN104355541B (en) | A kind of black slag crystallite stone material and preparation method thereof | |
| CN101525174A (en) | Compound coagulant made from fly ash and preparation method and application thereof | |
| CN105585039A (en) | Method for efficient and fast desilication of bauxite | |
| CN103288091A (en) | Method for preparing white carbon black by utilizing water glass with low modulus through carbonizing method of precipitation | |
| CN109207717A (en) | In sulfuric acid rare earth infusion and cleans and recycle the method for preparing high-purity mixed chlorinated rare earth | |
| CN105776870A (en) | Gold ore tailing manufactured ceramic glass board and manufacturing method thereof | |
| CN103232164B (en) | Coffee microcrystal glass plate and production method thereof | |
| CN104341107B (en) | A kind of glass batch and preparation method thereof and a kind of glass and preparation method thereof | |
| CN108455637A (en) | A kind of method of pre-desiliconizing with high alumina fly ash | |
| CN103819086B (en) | Method for preparing basic formula of soda-lime silicate glass and method for extracting aluminum from fly ash and co-producing glass | |
| CN107188209A (en) | The method that the hot method of the step alkali of andradite one handles middle-low bauxite production metallurgy grade aluminum oxide | |
| CN104341106B (en) | A kind of glass batch and preparation method thereof and a kind of glass and preparation method thereof | |
| CN103936045A (en) | Method for extracting aluminum oxide from coal ash | |
| CN104071984A (en) | Rolling technology for producing microcrystal glass plate by adopting fluorite tailing | |
| CN1994881A (en) | Method for preparing polysilicate aluminium molten iron processing agent using bauxite gangue | |
| CN106630644A (en) | Rare-earth slag glass-ceramic and preparation method thereof | |
| CN106565096B (en) | A method of devitrified glass is prepared using carbide slag | |
| CN102584042A (en) | Steel slag compound micro powder and preparation method thereof | |
| CN108658455A (en) | A kind of production method of high intensity mobile phone screen glass | |
| CN109809420B (en) | Preparation method of polymeric aluminum ferric silicate flocculant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee after: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee after: Beijing low carbon clean energy research institute Address before: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Shenhua building Patentee before: SHENHUA GROUP Corp.,Ltd. Patentee before: Beijing low carbon clean energy research institute |