CN105271784A - Hollow glass microsphere - Google Patents
Hollow glass microsphere Download PDFInfo
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- CN105271784A CN105271784A CN201510725293.4A CN201510725293A CN105271784A CN 105271784 A CN105271784 A CN 105271784A CN 201510725293 A CN201510725293 A CN 201510725293A CN 105271784 A CN105271784 A CN 105271784A
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- hollow glass
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- oxide
- glass micro
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- 239000011521 glass Substances 0.000 title claims abstract description 247
- 239000004005 microsphere Substances 0.000 title claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 171
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 59
- 239000000292 calcium oxide Substances 0.000 claims abstract description 53
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 53
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 49
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 45
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 35
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 21
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 15
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001950 potassium oxide Inorganic materials 0.000 claims abstract description 14
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000011806 microball Substances 0.000 claims description 190
- 239000007788 liquid Substances 0.000 claims description 130
- 239000002002 slurry Substances 0.000 claims description 109
- 239000000843 powder Substances 0.000 claims description 104
- 239000002243 precursor Substances 0.000 claims description 75
- 238000005245 sintering Methods 0.000 claims description 75
- 239000000243 solution Substances 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 62
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 56
- 239000002270 dispersing agent Substances 0.000 claims description 52
- 230000015572 biosynthetic process Effects 0.000 claims description 51
- 238000003786 synthesis reaction Methods 0.000 claims description 48
- 239000007787 solid Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 39
- 238000000889 atomisation Methods 0.000 claims description 34
- 238000007906 compression Methods 0.000 claims description 28
- 230000006835 compression Effects 0.000 claims description 28
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 27
- -1 polyoxyethylene Polymers 0.000 claims description 27
- 241000196324 Embryophyta Species 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000002309 gasification Methods 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 24
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 24
- 230000004083 survival effect Effects 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 18
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- 235000019353 potassium silicate Nutrition 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000011344 liquid material Substances 0.000 claims description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 14
- 239000003595 mist Substances 0.000 claims description 14
- 239000004317 sodium nitrate Substances 0.000 claims description 13
- 235000010344 sodium nitrate Nutrition 0.000 claims description 13
- 229940001516 sodium nitrate Drugs 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 13
- 150000001412 amines Chemical group 0.000 claims description 12
- 229910021538 borax Inorganic materials 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- 239000004328 sodium tetraborate Substances 0.000 claims description 12
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- 239000000741 silica gel Substances 0.000 claims description 10
- 229910002027 silica gel Inorganic materials 0.000 claims description 10
- 229910052728 basic metal Inorganic materials 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- 235000010216 calcium carbonate Nutrition 0.000 claims description 9
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000004111 Potassium silicate Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- 229920003169 water-soluble polymer Polymers 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 4
- 239000005388 borosilicate glass Substances 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 239000005368 silicate glass Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims 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 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005385 borate glass Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 claims description 2
- 239000005365 phosphate glass Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- NCGSLDXVMRCQPG-UHFFFAOYSA-K trisodium;carbonate;chloride Chemical compound [Na+].[Na+].[Na+].[Cl-].[O-]C([O-])=O NCGSLDXVMRCQPG-UHFFFAOYSA-K 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 4
- 238000001694 spray drying Methods 0.000 claims 3
- 238000009792 diffusion process Methods 0.000 claims 1
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- 239000002356 single layer Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 238000000227 grinding Methods 0.000 description 25
- 238000007667 floating Methods 0.000 description 22
- 239000003292 glue Substances 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 22
- 239000012071 phase Substances 0.000 description 17
- 229960001866 silicon dioxide Drugs 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000004115 Sodium Silicate Substances 0.000 description 10
- 229910052911 sodium silicate Inorganic materials 0.000 description 10
- 238000009413 insulation Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011805 ball Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000002928 artificial marble Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 229910052722 tritium Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000004223 radioprotective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
The invention discloses a hollow glass microsphere, which is prepared by a soft chemical method, wherein the thin wall of the hollow glass microsphere contains 55-88% of silicon dioxide (by weight), 3-30% of boron oxide (by weight), 2-32% of sodium oxide (by weight), 0-15% of calcium oxide (by weight), 0-5% of aluminum oxide (by weight), 0-5% of magnesium oxide (by weight), 0-5% of potassium oxide (by weight) and 0-2% of lithium oxide (by weight), and the density of the hollow glass microsphere is as follows: 0.1 to 0.7g/cm3. The hollow glass microsphere has high compressive strength, light weight, low alkali, water resistance, good fluidity and dispersibility, and thin and uniform wall.
Description
The application is Chinese Patent Application No. is 201210056295.5, and name is called the divisional application of the soft chemical preparation process of a kind of hollow glass micro-ball and made hollow glass micro-ball and application thereof
Technical field
The invention belongs to soft chemical method technical field, specifically, the present invention relates to a kind of silicon-dioxide and/or silicate solutions, colloidal sol or aqueous slurry of adopting and prepare hollow glass micro-ball and application thereof by soft chemical method.
Background technology
The light granules powder body material of hollow glass micro-ball HGM (HollowGlassMicrosphere) to be a kind of particle diameter be micron-sized spherical hollow structure, has that thermal insulation, insulation, sound insulation, high strength, wear-resisting, corrosion-resistant, radioprotective, water-intake rate are low, chemically stable, mobility and a dispersed feature such as excellent.It is primarily of silicate glass system composition in chemical composition, and preferential employing is the basic metal or the alkaline earth borosilicate compositional system that contain some oxide compound additives usually.Its Application Areas is very extensive in recent years, and main application fields has: light filling thing in various uses polymkeric substance; Paint and weighting material in coated material; Prepare dielectric material that is heat insulation, sound insulation; The insulating coating material of open storage surface layer; Lighting structured material weighting agent during space flight and aviation and marine technology design; The deep water technology buoyancy material of ocean exploitation research; The matrix material of high strength, indeformable alloy in lightweight and hollow glass micro-ball; For automotive industry is that the material of the various uses of base-material is as bodywork parts, inside fitting, sealing agent, putty and putty etc. with hollow glass micro-ball; Emulsion explosive Midst density and capability of antidetonance conditioning agent; Electric elements casing insulation and radar scanner coated material in electronic industry; The pellet carrier of the filling deuterium tritium gas mixture of nucleosynthesis; The packing material of artificial marble, artificial timber; Thermal insulation material in low temperature technique; For the hollow glass micro-ball of the high compressive strength of oilfield, etc.
In order to meet the demand of each field application, describe chemical composition and the high yield, efficiently engineering equipment details of corresponding manufacturing process technology and microballoon in numerous patents.Manufacture in patented technology at numerous hollow glass micro-balls, be applied to the solid phase glass powder method of manufacturing technology mainly Minnesota Mining and Manufacturing Company's employing at present and the liquid phase atomization method of Pq Corp. of U.S. employing of suitability for industrialized production hollow glass micro-ball.Nowadays these two kinds of methods obtain widespread use.These two kinds of processing methodes are that the hollow glass micro-ball tandem product in preparation different application field provides many industrialization manufacture approach.They are not only different in device structure, profile, and the physical-chemical reaction simultaneously in manufacturing process and in the material adopted and technological process is also different.About solid phase glass powder law technology route, 60 to the eighties of last century, 3M company at U. S. application a lot of patent as United States Patent (USP) 3129086,3230064,3365315,4391646, be described in detail, and applied for patent of invention CN101068753A in 2005 in China, processing technology routine roughly the same also has CN101638295A.Solid phase glass powder method processing technology routine principal character is: first glass system Solid raw materials is added whipping agent high-temperature fusion, then shrend, grinds, and crosses screen sizing and obtains thick product, form hollow glass micro-ball through high temperature foaming again, required high temperature is 1200 ~ 1600 DEG C.Because the work in-process adopting high temperature solid state reaction to produce hollow glass micro-ball not only need high temperature (being greater than 1200 DEG C) melt stage, and need by grinding process, therefore production energy consumption is large, technological cycle is long, and size-grade distribution is wayward, especially produces particle diameter thinner, the kind that density is lighter, can increase a lot of difficulty, required energy consumption can increase, and cost is high.
Come from the description of United States Patent (USP) 2797201 the earliest for hollow glass micro-ball about liquid phase atomization legal system.This technology adopts borsyl to be that the drying of raw material Direct spraying obtains the low-density hollow glass micro-ball product of not vitrified strong basicity, and the method products obtained therefrom is very strong because of alkalescence, be very easily dissolved in water, and ultimate compression strength is very low.For this reason, at United States Patent (USP) 3699050,3794503,3796777, describe in 3888957 and adopt mixed aqueous solution such as formation such as interpolation boric acid and its esters etc. to reach the object that reduction alkalescence improves hollow glass micro-ball water tolerance in sodium silicate aqueous solution, obtain the hollow glass micro-ball product with certain water tolerance.Although products obtained therefrom has preferably dispersed and lower tap density, fundamentally do not change the not vitrified state of product, cause that product still easily absorbs water, intensity difference.Because hollow glass micro-ball exists very high free energy and surfactivity, particle is soft-agglomerated and caking easily, thus causes particle spheroid in packaging and the course of processing easily broken.In addition, United States Patent (USP) 3915735,4134848,4141751 also illustrate by carrying out at hollow glass micro-ball Surface coating differing materials the integrity that the post-treating methods such as modification improve microballoon, but its defect is that to want to obtain even complete packet coating very difficult, and the problem of unresolved hollow glass micro-ball intensity difference, be difficult in treating processes in this post avoid microballoon not to be broken.In United States Patent (USP) 4540629, describe in-stiu coating technology attempt to solve the dispersiveness of liquid phase atomization method hollow glass micro-ball and the problem of poor water resistance, but owing to lacking the vitrified operation of microballoon in liquid phase atomization method operation, so microballoon still can not reach desirable ultimate compression strength.United States Patent (USP) 5534348 describes new process program for this reason: density is 0.6g/cm3, particle diameter is 30 ~ 40 microns of precursor powders namely to adopt solid content to be the water glass of 25 ~ 40% (weight) and borax mixed aqueous solution to be the direct centrifugal spraying of raw material to obtain, be incorporated into after again this powder being ground in the heat pipe being referred to as to dodge quick-fried device, the hollow glass micro-ball of borsyl can be formed through 600 ~ 700 ℉ thermal treatments.But because raw materials used system is strong basicity material as described in that patent, intermediates need through grinding technics, though (more than 400 DEG C) thermal treatment at a lower temperature, still be difficult to vitrifying complete, the critical defect of its product is that alkalescence is large, and intensity is low, easy water suction, reunites.
Be not difficult to find that liquid phase atomization law technology major advantage is: 1. energy consumption is low, and technique does not exist high-temperature fusion process.2. flow process is short, without the need to pulverizing grinding classification molten sintering.3. cost is low.The people such as Zhang Jingjie in 1997 describe " making raw material with the fine ceramics slurries through wet chemical method process gained " in patent CN1071721C, this slurries component is " containing fine ceramics powder, shaping assistant, water-soluble polymer tackiness agent and water " to " gained slurries carry out drying, and be dried the powder being processed into 20 ~ 150 microns ", namely gained powder obtains " transparent ceramic micro-bead " " sintering under 1000 DEG C ~ 1500 DEG C conditions ", this microballon is solid glass microballoon, specify " method technique be suitable for equally produce other functional " glass microsphere material of this invention in that patent.But do not relate to concrete component and the process of preparing of hollow glass micro-ball in this patent.Therefore, the preparation method that a kind of hollow glass micro-ball and hollow glass micro-ball thereof are provided is needed.
Summary of the invention
First technical problem that will solve of the present invention is to provide a kind of hollow glass micro-ball, and hollow glass micro-ball ultimate compression strength is high, lightweight, and low alkali is water-fast, mobility, good dispersity.
For solving the problems of the technologies described above, the present invention adopts following technical proposals:
A kind of hollow glass micro-ball, this hollow glass micro-ball is prepared from as follows:
The feed liquid system synthesis of the first step hollow glass micro-ball: adopt solution, colloidal sol or homodisperse aqueous slurry as feed liquid system, this feed liquid system contains SiO
2and/or containing SiO
2basic metal or the silicate solutions of alkaline-earth metal, colloidal sol or slurries material, inorganic salt material, stable dispersant and water, wherein SiO
2and/or containing SiO
2basic metal or the silicate solutions of alkaline-earth metal, colloidal sol or slurries material shared by the ratio of whole feed liquid system be 6 ~ 30% (weight), the ratio of whole feed liquid system shared by inorganic salt material is 3 ~ 25% (weight), the ratio of whole feed liquid system shared by stable dispersant is 0.1 ~ 2% (weight), and surplus is water; The feed liquid system synthesis step of hollow glass micro-ball is as follows:
According to ratio (weight) shared in feed liquid system by the SiO of 6 ~ 30%
2and/or containing SiO
2basic metal or the silicate solutions of alkaline-earth metal, colloidal sol or water slurry liquid material and 3 ~ 25% inorganic salt material be mixed with solution, colloidal sol or water slurry liquid material, then under 30 ~ 80 DEG C and normal pressure, it is fully mixed, through reaction, add the solution or colloidal sol or slurries that obtain homogeneous after 0.1 ~ 2% stable dispersant homogenizes again, make the solid grain size size in the slurries of formation guarantee at least to be less than less than 2 microns;
Second step class spherical precursor powder synthesizes: the solution the homogenized the first step obtained or colloidal sol or slurries obtain the spherical precursor powder of micron order class by atomization quick dewatering drying method;
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder can be obtained by 600 ~ 1100 DEG C of vitrifying sintering processes the micron order hollow glass micro-ball that volume its floatability is greater than 90%; Made hollow glass micro-ball is that micron order inside is full of the hollow and thin-walled glass microsphere of gas, dioxide-containing silica (weight) 55 ~ 88% in thin-walled, its true density is 0.1 ~ 0.7g/cm3,80% survival content time ultimate compression strength be 1 ~ 50MPa.
The preparation method of described hollow glass micro-ball comprises the 4th step surface modification further, and the method for described surface modification comprises solution method or spray method.Wherein, solution method: by the aqueous solution of superpolymer or the aqueous solution of coupling agent acid-conditioning solution pH value to 2 ~ 5, then add hollow glass micro-ball, reaction 0.5 ~ 8 hour at room temperature ~ 80 DEG C, filters, drying obtains the hollow glass micro-ball after surface modification; Or spray method: by the aqueous solution of coupling agent acid-conditioning solution pH value to 2 ~ 5, atomization spray in hollow glass micro-ball surface, then carry out follow-up drying treatment obtain surface modification after hollow glass micro-ball.
Described SiO
2for gas-phase silica, precipitated silica, silicon sol, silica gel micro mist or superfine quartz sand micro mist; Described containing SiO
2basic metal or the silicate of alkaline-earth metal comprise Starso, water glass, water glass potassium, potassium silicate, lithium silicate or silicic acid quaternary amine; Described stable dispersant comprises tensio-active agent or high molecular weight water soluble polymer.
Described inorganic salt material is water-soluble and/or water-insoluble boron, sodium, calcium, aluminium, magnesium, the inorganic salt of potassium or lithium, comprise: boric acid, borax, ammonium borate, sodium-chlor, sodium carbonate, SODIUMNITRATE, sodium sulfate, calcium chloride, calcium carbonate, nitrocalcite, calcium hydroxide, aluminum chloride, aluminum nitrate, Tai-Ace S 150, magnesium chloride, magnesium nitrate, magnesium sulfate, salt of wormwood, saltpetre, potassium sulfate, potassium hydroxide, lithium nitrate, Quilonum Retard or hydronium(ion) Lithium Oxide 98min, kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide: 3-30%, sodium oxide: 0-32%, calcium oxide: 0-15%, aluminum oxide: 0-5%, magnesium oxide: 0-5%, potassium oxide: 0-5%, Lithium Oxide 98min: 0-2%.
Described high molecular weight water soluble polymer is polyoxyethylene glycol, polyacrylamide, polyoxyethylene or polyvinyl alcohol.
The feed liquid system of described hollow glass micro-ball also comprises ultra-low-alkali borosilicate glass system, alkaline earth borosilicate glass system, alumina silicate glass system, aluminum borate glass system, phosphate glass system or aluminum oxide, zirconium white diluted system.
Dioxide-containing silica (weight) 55 ~ 88% in the thin-walled of described hollow glass micro-ball, boron oxide (weight) 3 ~ 30%, sodium oxide (weight) 2 ~ 32%, calcium oxide (weight) 0 ~ 15%, aluminum oxide (weight) 0 ~ 5%, magnesium oxide (weight) 0 ~ 5%, potassium oxide (weight) 0 ~ 5%, Lithium Oxide 98min (weight) 0 ~ 2%, its density is: 0.1 ~ 0.7g/cm
3.
Hollow glass micro-ball of the present invention can be used as light filling thing in various uses polymkeric substance; Paint and weighting material in coated material; Prepare dielectric material that is heat insulation, sound insulation; The insulating coating material of open storage surface layer; Lighting structured material weighting agent during space flight and aviation and marine technology design; The deep water technology buoyancy material of ocean exploitation research; The matrix material of high strength, indeformable alloy in lightweight and hollow glass micro-ball; Automotive industry be that the material of the various uses of base-material is as bodywork parts, interior material, sealing agent, putty and putty etc. with hollow glass micro-ball; The density of emulsion explosive and capability of antidetonance conditioning agent; Electric elements casing insulation and radar scanner coated material in electronic industry; The pellet carrier of the filling deuterium tritium gas mixture of nucleosynthesis; The packing material of artificial marble, artificial timber; Thermal insulation material in low temperature technique; The well cementation of the high compressive strength of oilfield, drilling well, flotation material.。
Beneficial effect of the present invention is as follows:
The present invention relates to the hollow glass micro-ball that a kind of softening method manufactures.This hollow glass micro-ball ultimate compression strength is high, lightweight, low alkali is water-fast, mobility, good dispersity, and wall is thin evenly (as shown in Figure 4).
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 illustrates that hollow glass micro-ball of the present invention preparation is softening and learns technological process flow process figure.
Fig. 2 illustrates hollow glass micro-ball particle size distribution figure prepared by embodiment 2.
Fig. 3 illustrates hollow glass micro-ball light micrograph of the present invention.
Fig. 4 illustrates hollow glass micro-ball wall thickness stereoscan photograph of the present invention.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.Parts similar in accompanying drawing represent with identical Reference numeral.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
Embodiment 1
The feed liquid system synthesis of the first step hollow glass micro-ball:
The slurries of the 4000g containing 600g gas-phase silica and 485g sodium silicate solution (are included silica 1 21g, sodium oxide 39g) include 60g borax with 517g, 60g SODIUMNITRATE, 90g calcium carbonate, 40g magnesium chloride, 40g saltpetre, the solution of 20g Quilonum Retard becomes water slurry liquid material, then under 30 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 10g stable dispersant polyoxyethylene again, the slurries homogenized are formed through colloidal mill grinding, the solid grain size size in slurries is made at least to be less than less than 2 microns.Wherein, gas-phase silica and water glass shared part by weight in feed liquid is 15.2%, inorganic salt shared part by weight in feed liquid is 6.2%, stable dispersant shared part by weight in feed liquid is 0.2%, kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B2O3:4.4%, sodium oxide Na
2o:3.9%, calcium oxide CaO:5.4%, magnesium oxide MgO:1.8%, potassium oxide K
2o:2.0%, Lithium Oxide 98min Li
2o:0.9%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 320 DEG C, temperature out 120 DEG C, obtains the spherical precursor powder of class of 20 ~ 150 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 800 DEG C ~ 1000 DEG C, the hollow glass micro-ball product that median size is 38um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 79.8% in hollow glass micro-ball thin-walled, boron oxide (weight) 2.2%, sodium oxide (weight) 7.6%, calcium oxide (weight) 5.6%, magnesium oxide (weight) 1.8%, potassium oxide (weight) 2.1%, Lithium Oxide 98min (weight) 0.9%.The true density of hollow glass micro-ball is 0.55g/cm3, ultimate compression strength (80% survival content) is 42MPa.
Embodiment 2
The feed liquid system synthesis of the first step hollow glass micro-ball:
The slurries of the 4000g containing gas-phase silica 600g and 364g sodium silicate solution (are included silicon-dioxide 91g, sodium oxide 29g) with 350g include 40g borax, 60g sodium sulfate, 90g nitrocalcite, 20g saltpetre solution become water slurry liquid material, then under 30 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 5.5g stable dispersant polyoxyethylene again, form through colloidal mill grinding the slurries homogenized, make the solid grain size size in slurries at least be less than less than 2 microns.Wherein, gas-phase silica and water glass shared part by weight in feed liquid is 15.3%, inorganic salt shared part by weight in feed liquid is 4.5%, stable dispersant shared part by weight in feed liquid is 0.12%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 3.4%, sodium oxide Na
2o:4.4%, calcium oxide CaO:2.6%, potassium oxide K
2o:1.1%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 380 DEG C, temperature out 140 DEG C, obtains the spherical precursor powder of class of 5 ~ 120 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 900 DEG C ~ 1100 DEG C, the hollow glass micro-ball product that median size is 30um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 86.5% in hollow glass micro-ball thin-walled, boron oxide (weight) 1.7%, sodium oxide (weight) 7.4%, calcium oxide (weight) 3.1%, potassium oxide (weight) 1.3%.The true density of hollow glass micro-ball is 0.60g/cm3, ultimate compression strength (80% survival content) is 50MPa.
Embodiment 3
The feed liquid system synthesis of the first step hollow glass micro-ball:
The slurries of the 3333g containing gas-phase silica 500g and 198g sodium-potassium silicate solution (are included silicon-dioxide 53.3g, sodium oxide 8.9g, potassium oxide 17.8) include 60g boric acid with 440g, 50g sodium sulfate, 90g calcium carbonate, the solution of 20g magnesium sulfate becomes water slurry liquid material, then under 80 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 5.0g stable dispersant polyoxyethylene again, the slurries homogenized are formed through colloidal mill grinding, the solid grain size size in slurries is made at least to be less than less than 2 microns.Wherein, gas-phase silica and sodium-potassium silicate shared part by weight in feed liquid is 14.6%, inorganic salt shared part by weight in feed liquid is 5.5%, stable dispersant shared part by weight in feed liquid is 0.13%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 4.8%, sodium oxide Na
2o:3.0%, calcium oxide CaO:7.3%, magnesium oxide MgO:1.0%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 310 DEG C, temperature out 120 DEG C, obtains the spherical precursor powder of class of 20 ~ 100 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 900 DEG C ~ 1100 DEG C, the hollow glass micro-ball product that median size is 35um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 82.8% in hollow glass micro-ball thin-walled, boron oxide (weight) 2.4%, sodium oxide (weight) 3.6%, calcium oxide (weight) 7.6%, magnesium oxide (weight) 1.0%, potassium oxide (weight) 2.6%.The true density of hollow glass micro-ball is 0.50g/cm3, ultimate compression strength (80% survival content) is 33MPa.
Embodiment 4
The feed liquid system synthesis of the first step hollow glass micro-ball:
Slurries and the 1100g of the 2000g containing precipitated silica 200g are included 200g boric acid, 200g SODIUMNITRATE, 50g magnesium nitrate, 50g nitrocalcite, 50g aluminum nitrate solution become water slurry liquid material, then under 80 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 6.2g stable dispersant polyoxyethylene again, form through colloidal mill grinding the slurries homogenized, make the solid grain size size in slurries at least be less than less than 2 microns.Wherein, precipitated silica shared part by weight in feed liquid is 6.4%, inorganic salt shared part by weight in feed liquid is 17.7%, stable dispersant shared part by weight in feed liquid is 0.2%, kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B2O3:27.2%, sodium oxide Na
2o:17.9%, magnesium oxide MgO:1.9%, calcium oxide CaO:2.9%, aluminium oxide Al
2o
3: 1.7%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 350 DEG C, temperature out 130 DEG C, obtains the spherical precursor powder of class of 50 ~ 100 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 600 DEG C ~ 800 DEG C, the hollow glass micro-ball product that median size is 35um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 59.8% in hollow glass micro-ball thin-walled, boron oxide (weight) 13.6%, sodium oxide (weight) 16.1%, magnesium oxide (weight) 2.9%, calcium oxide (weight) 4.9%, aluminum oxide (weight) 2.7%.The true density of hollow glass micro-ball is 0.30g/cm
3, ultimate compression strength (80% survival content) is 5MPa.
Embodiment 5
The feed liquid system synthesis of the first step hollow glass micro-ball:
Colloidal sol and the 540g of the 2500g containing silica gel micro mist 250g are included 120g boric acid, 100g SODIUMNITRATE, 50g magnesium nitrate solution become colloidal sol, then under 80 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 6.0g stable dispersant polyoxyethylene again, form through colloidal mill grinding the slurries homogenized.Wherein, silica gel micro mist shared part by weight in feed liquid is 8.2%, inorganic salt shared part by weight in feed liquid is 8.8%, stable dispersant shared part by weight in feed liquid is 0.2%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 18.6%, sodium oxide Na
2o:10.2%, magnesium oxide MgO:2.2%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 360 DEG C, temperature out 130 DEG C, obtains the spherical precursor powder of class of 50 ~ 100 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 800 DEG C ~ 1000 DEG C, the hollow glass micro-ball product that median size is 38um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 78.3% in hollow glass micro-ball thin-walled, boron oxide (weight) 9.3%, sodium oxide (weight) 9.2%, magnesium oxide (weight) 3.2%.The true density of hollow glass micro-ball is 0.40g/cm
3, ultimate compression strength (80% survival content) is 25MPa.
Embodiment 6
The feed liquid system synthesis of the first step hollow glass micro-ball:
The 1905g slurries and 545g sodium silicate solution that contain gas-phase silica 286g (are included silica 1 36g, sodium oxide 44g) include 80g ammonium borate with 167g, the solution of 20g SODIUMNITRATE becomes water slurry liquid material, then under 30 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 5.2g stable dispersant polyoxyethylene again, form the slurries homogenized through ball mill grinding, make the solid grain size size in slurries at least be less than less than 2 microns.Wherein, gas-phase silica and water glass shared part by weight in feed liquid is 17.8%, inorganic salt shared part by weight in feed liquid is 3.8%, stable dispersant shared part by weight in feed liquid is 0.2%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 9.5%, sodium oxide Na
2o:1.3%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 350 DEG C, temperature out 130 DEG C, obtains the spherical precursor powder of class of 30 ~ 120 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 850 DEG C ~ 1050 DEG C, the hollow glass micro-ball product that median size is 40um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 86.5% in hollow glass micro-ball thin-walled, boron oxide (weight) 4.7%, sodium oxide (weight) 8.8%.The true density of hollow glass micro-ball is 0.30g/cm
3, ultimate compression strength (80% survival content) is 9MPa.
Embodiment 7
The feed liquid system synthesis of the first step hollow glass micro-ball:
By include containing the colloidal sol of 2000g of silicon sol 300g and 163g silicic acid quaternary amine solution (including silica 1 16g) and 533g 110g borax, 120g sodium sulfate, 90g calcium carbonate solution become colloidal sol, then under 40 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 6g stable dispersant polyoxyethylene again, form the slurries homogenized through ball mill grinding.Wherein, silicon sol and silicic acid quaternary amine shared part by weight in feed liquid is 15.0%, inorganic salt shared part by weight in feed liquid is 10.7%, stable dispersant shared part by weight in feed liquid is 0.2%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 12.2%, sodium oxide Na
2o:13.8%, calcium oxide CaO:8.0%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 310 DEG C, temperature out 120 DEG C, obtains the spherical precursor powder of class of 40 ~ 90 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 800 DEG C ~ 1000 DEG C, the hollow glass micro-ball product that median size is 50um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 72.1% in hollow glass micro-ball thin-walled, boron oxide (weight) 6.1%, sodium oxide (weight) 12.4%, calcium oxide (weight) 9.4%, the true density of hollow glass micro-ball is 0.25g/cm
3, ultimate compression strength (80% survival content) is 2.0MPa.
Embodiment 8
The feed liquid system synthesis of the first step hollow glass micro-ball:
By include containing the colloidal sol of 2000g of silicon sol 300g and 448g silicic acid quaternary amine solution (including silicon-dioxide 318g) and 417g 90g borax, 110g sodium carbonate, 50g calcium hydroxide solution become colloidal sol, then under 40 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 7.3g stable dispersant polyoxyethylene again, form the slurries homogenized through ball mill grinding.Wherein, silicon sol and silicic acid quaternary amine shared part by weight in feed liquid is 19.3%, inorganic salt shared part by weight in feed liquid is 6.9%, stable dispersant shared part by weight in feed liquid is 0.2%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 7.6%, sodium oxide Na
2o:11.4%, calcium oxide CaO:4.7%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 320 DEG C, temperature out 125 DEG C, obtains the spherical precursor powder of class of 40 ~ 90 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 800 DEG C ~ 1000 DEG C, the hollow glass micro-ball product that median size is 40um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 80.9% in hollow glass micro-ball thin-walled, boron oxide (weight) 3.8%, sodium oxide (weight) 10.2%, calcium oxide (weight) 5.1%, the true density of hollow glass micro-ball is 0.25g/cm
3, ultimate compression strength (80% survival content) is 2.0MPa.
Embodiment 9
The feed liquid system synthesis of the first step hollow glass micro-ball:
The slurries of the 136g containing superfine quartz sand micro mist 20g and 1030g sodium silicate solution (are included silicon-dioxide 258g, sodium oxide 82g) include 40g borax with 167g, the solution of 60g sodium sulfate becomes water slurry liquid material, then under 30 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 2.7g stable dispersant polyoxyethylene again, form the slurries homogenized through ball mill grinding, make the solid grain size size in slurries at least be less than less than 2 microns.Wherein, superfine quartz sand micro mist and water glass shared part by weight in feed liquid is 27%, inorganic salt shared part by weight in feed liquid is 7.5%, stable dispersant shared part by weight in feed liquid is 0.2%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 3.3%, sodium oxide Na
2o:9.7%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 320 DEG C, temperature out 125 DEG C, obtains the spherical precursor powder of class of 30 ~ 120 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 700 DEG C ~ 900 DEG C, the hollow glass micro-ball product that median size is 40um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 71.6% in hollow glass micro-ball thin-walled, boron oxide (weight) 1.7%, sodium oxide (weight) 26.7%.The true density of hollow glass micro-ball is 0.35g/cm
3, ultimate compression strength (80% survival content) is 6MPa.
Embodiment 10
The feed liquid system synthesis of the first step hollow glass micro-ball:
The 408g slurries and 545g sodium silicate solution that contain gas-phase silica 61g (are included silica 1 36g, sodium oxide 44g) include 20g ammonium borate with 67g, the solution of 20g sodium sulfate becomes water slurry liquid material, then under 30 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 2.0g stable dispersant polyoxyethylene again, form the slurries homogenized through ball mill grinding, make the solid grain size size in slurries at least be less than less than 2 microns.Wherein, gas-phase silica and water glass shared part by weight in feed liquid is 23.6%, inorganic salt shared part by weight in feed liquid is 3.9%, stable dispersant shared part by weight in feed liquid is 0.2%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 4.7%, sodium oxide Na
2o:3.2%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 300 DEG C, temperature out 120 DEG C, obtains the spherical precursor powder of class of 30 ~ 120 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 750 DEG C ~ 950 DEG C, the hollow glass micro-ball product that median size is 35um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 79.7% in hollow glass micro-ball thin-walled, boron oxide (weight) 2.3%, sodium oxide (weight) 18.0%.The true density of hollow glass micro-ball is 0.40g/cm
3, ultimate compression strength (80% survival content) is 16MPa.
Embodiment 11
The feed liquid system synthesis of the first step hollow glass micro-ball:
The 889g colloidal sol and 545g sodium silicate solution that contain silica gel micro mist 133g (are included silica 1 36g, sodium oxide 44g) with 317g include 80g borax, 80g SODIUMNITRATE, 30g calcium carbonate solution become the water-sol, then under 30 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 3.5g stable dispersant polyoxyethylene again, form through homogeneous emulsifying machine grinding the slurries homogenized.Wherein, silica gel micro mist and water glass shared part by weight in feed liquid is 17.9%, inorganic salt shared part by weight in feed liquid is 10.9%, stable dispersant shared part by weight in feed liquid is 0.2%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 12.9%, sodium oxide Na
2o:12.6%, calcium oxide CaO:3.9%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 310 DEG C, temperature out 120 DEG C, obtains the spherical precursor powder of class of 30 ~ 120 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 750 DEG C ~ 950 DEG C, the hollow glass micro-ball product that median size is 35um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 68.7% in hollow glass micro-ball thin-walled, boron oxide (weight) 6.5%, sodium oxide (weight) 20.6%, calcium oxide (weight) 4.2%.The true density of hollow glass micro-ball is 0.30g/cm
3, ultimate compression strength (80% survival content) is 8MPa.
Embodiment 12
The feed liquid system synthesis of the first step hollow glass micro-ball:
The aqueous solution of the 2100g containing precipitated silica 316g and 1061g silicic acid quaternary amine solution (including silicon-dioxide 273g) are included 40g ammonium borate with 350g, 80g sodium carbonate, 30g calcium hydroxide, 20g aluminum chloride, the solution form slurry of 40g magnesium chloride, then under 40 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 7.0g stable dispersant polyoxyethylene again, the slurries homogenized are formed through homogeneous emulsifying machine grinding, the solid grain size size in slurries is made at least to be less than less than 2 microns.Wherein, precipitated silica and silicic acid quaternary amine shared part by weight in feed liquid is 18.9%, inorganic salt shared part by weight in feed liquid is 6.0%, stable dispersant shared part by weight in feed liquid is 0.2%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 3.5%, sodium oxide Na
2o:6.7%, calcium oxide CaO:1.2%, aluminium oxide Al
2o
3: 0.3%, magnesium oxide MgO:2.4%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 320 DEG C, temperature out 120 DEG C, obtains the spherical precursor powder of class of 40 ~ 90 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 900 DEG C ~ 1100 DEG C, the hollow glass micro-ball product that median size is 38um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 85.1% in hollow glass micro-ball thin-walled, boron oxide (weight) 1.8%, sodium oxide (weight) 6.0%, calcium oxide (weight) 4.6%, aluminum oxide (weight) 0.3%, magnesium oxide (weight) 2.2%, the true density of hollow glass micro-ball is 0.50g/cm
3, ultimate compression strength (80% survival content) is 40MPa.
Embodiment 13
The feed liquid system synthesis of the first step hollow glass micro-ball:
The aqueous solution of the 2456g containing precipitated silica 368g and 455g silicic acid quaternary amine solution (including silica 1 17g) are included the solution form slurry of 80g borax, 20g sodium carbonate, 30g nitrocalcite, 20g Tai-Ace S 150,20g magnesium sulfate with 283g, then under 40 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 32g stable dispersant polyoxyethylene again, form through homogeneous emulsifying machine grinding the slurries homogenized, make the solid grain size size in slurries at least be less than less than 2 microns.Wherein, precipitated silica and silicic acid quaternary amine shared part by weight in feed liquid is 16.2%, inorganic salt shared part by weight in feed liquid is 5.3%, stable dispersant shared part by weight in feed liquid is 1%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 9.6%, sodium oxide Na
2o:6.3%, calcium oxide CaO:1.2%, aluminium oxide Al
2o
3: 0.5%, magnesium oxide MgO:1.2%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 320 DEG C, temperature out 120 DEG C, obtains the spherical precursor powder of class of 40 ~ 90 microns;
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 900 DEG C ~ 1100 DEG C, the hollow glass micro-ball product that median size is 35um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 85.9% in hollow glass micro-ball thin-walled, boron oxide (weight) 4.8%, sodium oxide (weight) 5.7%, calcium oxide (weight) 1.5%, aluminum oxide (weight) 0.6%, magnesium oxide (weight) 1.5%, the true density of hollow glass micro-ball is 0.35g/cm
3, ultimate compression strength (80% survival content) is 15MPa.
Embodiment 14
The feed liquid system synthesis of the first step hollow glass micro-ball:
The aqueous solution of the 1053g containing precipitated silica 158g and 1364g silicic acid quaternary amine solution (including silicon-dioxide 351g) are included the solution form slurry of 80g borax, 20g sodium carbonate, 90g calcium carbonate with 317g, then under 40 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 27g stable dispersant polyoxyethylene again, form through homogeneous emulsifying machine grinding the slurries homogenized, make the solid grain size size in slurries at least be less than less than 2 microns.Wherein, precipitated silica and silicic acid quaternary amine shared part by weight in feed liquid is 22.2%, inorganic salt shared part by weight in feed liquid is 7.0%, stable dispersant shared part by weight in feed liquid is 1%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 8.6%, sodium oxide Na
2o:5.0%, calcium oxide CaO:7.8%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 360 DEG C, temperature out 135 DEG C, obtains the spherical precursor powder of class of 40 ~ 90 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 850 DEG C ~ 1050 DEG C, the hollow glass micro-ball product that median size is 38um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 82.5% in hollow glass micro-ball thin-walled, boron oxide (weight) 4.3%, sodium oxide (weight) 4.5%, calcium oxide (weight) 8.7%, the true density of hollow glass micro-ball is 0.35g/cm
3, ultimate compression strength (80% survival content) is 15MPa.
4th step solution method surface modification: by the aqueous solution acid-conditioning solution pH value to 2 of superpolymer polyoxyethylene glycol (PEG-10000), add hollow glass micro-ball again, at room temperature react 0.5 hour, filtration, drying obtain the hollow glass micro-ball after surface modification.
Embodiment 15
The feed liquid system synthesis of the first step hollow glass micro-ball:
Slurries and the 12.0kg of the 40.0kg containing precipitated silica 4.0kg are included 2.2kg boric acid, 1.8kg SODIUMNITRATE, 0.25kg magnesium nitrate, 1.5kg nitrocalcite, 0.25kg aluminum nitrate solution become water slurry liquid material, then under 80 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 104g stable dispersant polyoxyethylene again, form through colloidal mill grinding the slurries homogenized, make the solid grain size size in slurries at least be less than less than 2 microns.Wherein, precipitated silica shared part by weight in feed liquid is 7.8%, inorganic salt shared part by weight in feed liquid is 11.0%, stable dispersant shared part by weight in feed liquid is 0.2%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 19.5%, sodium oxide Na
2o:10.5%, magnesium oxide MgO:0.6%, calcium oxide CaO:5.7%, aluminium oxide Al
2o
3: 0.6%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 320 DEG C, temperature out 125 DEG C, obtains the spherical precursor powder of class of 50 ~ 100 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 750 DEG C ~ 950 DEG C, the hollow glass micro-ball product that median size is 35um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 70.9% in hollow glass micro-ball thin-walled, boron oxide (weight) 9.7%, sodium oxide (weight) 9.5%, magnesium oxide (weight) 0.8%, calcium oxide (weight) 8.3%, aluminum oxide (weight) 0.8%.The true density of hollow glass micro-ball is 0.46g/cm
3, ultimate compression strength (80% survival content) is 40MPa.
Embodiment 16
The feed liquid system synthesis of the first step hollow glass micro-ball:
Slurries and the 8.2kg of the 22.0kg containing precipitated silica 2.4kg are included 1.5kg boric acid, 2.0kg SODIUMNITRATE, 0.2kg magnesium nitrate, 0.2kg nitrocalcite, 0.2kg aluminum nitrate solution become water slurry liquid material, then under 80 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 63g stable dispersant polyoxyethylene again, form through colloidal mill grinding the slurries homogenized, make the solid grain size size in slurries at least be less than less than 2 microns.Wherein, precipitated silica shared part by weight in feed liquid is 7.3%, inorganic salt shared part by weight in feed liquid is 13.6%, stable dispersant shared part by weight in feed liquid is 0.2%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 21.6%, sodium oxide Na
2o:18.8%, magnesium oxide MgO:0.8%, calcium oxide CaO:1.2%, aluminium oxide Al
2o
3: 0.7%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 320 DEG C, temperature out 125 DEG C, obtains the spherical precursor powder of class of 50 ~ 100 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 750 DEG C ~ 950 DEG C, the hollow glass micro-ball product that median size is 35um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 65.7% in hollow glass micro-ball thin-walled, boron oxide (weight) 10.8%, sodium oxide (weight) 17.1%, magnesium oxide (weight) 1.7%, calcium oxide (weight) 3.0%, aluminum oxide (weight) 1.7%.The true density of hollow glass micro-ball is 0.46g/cm
3, ultimate compression strength (80% survival content) is 43MPa.
Embodiment 17
The feed liquid system synthesis of the first step hollow glass micro-ball:
The slurries of the 35.0kg containing precipitated silica 3.5kg and 2.0kg sodium silicate solution (are included silicon-dioxide 0.5kg, sodium oxide 0.16kg) include 2.0kg boric acid with 11.0kg, 1.8kg SODIUMNITRATE, 0.25kg magnesium nitrate, 1.2kg nitrocalcite, 0.25kg aluminum nitrate, the solution of 1.5kg nitric acid becomes water slurry liquid material, then under 80 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 88g stable dispersant polyoxyethylene again, the slurries homogenized are formed through colloidal mill grinding, the solid grain size size in slurries is made at least to be less than less than 2 microns.Wherein, water glass and precipitated silica shared part by weight in feed liquid is 7.4%, inorganic salt shared part by weight in feed liquid is 12.9%, stable dispersant shared part by weight in feed liquid is 0.2%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 20.2%, sodium oxide Na
2o:12.8%, magnesium oxide MgO:0.7%, calcium oxide CaO:5.2%, aluminium oxide Al
2o
3: 0.6%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 320 DEG C, temperature out 125 DEG C, obtains the spherical precursor powder of class of 50 ~ 100 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 750 DEG C ~ 950 DEG C, the hollow glass micro-ball product that median size is 35um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 68.1% in hollow glass micro-ball thin-walled, boron oxide (weight) 10.1%, sodium oxide (weight) 11.7%, magnesium oxide (weight) 1.2%, calcium oxide (weight): 7.7%, aluminum oxide (weight): 1.2%.The true density of hollow glass micro-ball is 0.46g/cm
3, ultimate compression strength (80% survival content) is 40MPa.
Embodiment 18
The feed liquid system synthesis of the first step hollow glass micro-ball:
The 1481g colloidal sol and 424g sodium silicate solution that contain silica gel micro mist 222g (are included silica 1 06g, sodium oxide 34g) with 117g include 20g borax, 20g SODIUMNITRATE, 30g calcium carbonate solution become colloidal sol, then under 30 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 20g stable dispersant polyoxyethylene again, form through colloidal mill grinding the slurries homogenized.Wherein, silica gel micro mist and water glass shared part by weight in feed liquid is 17.9%, inorganic salt shared part by weight in feed liquid is 3.5%, stable dispersant shared part by weight in feed liquid is 1%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 3.2%, sodium oxide Na
2o:1.8%, calcium oxide CaO:4.5%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 320 DEG C, temperature out 120 DEG C, obtains the spherical precursor powder of class of 30 ~ 120 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 850 DEG C ~ 1050 DEG C, the hollow glass micro-ball product that median size is 35um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 83.5% in hollow glass micro-ball thin-walled, boron oxide (weight) 1.6%, sodium oxide (weight) 9.8%, calcium oxide (weight) 5.1%.The true density of hollow glass micro-ball is 0.45g/cm
3, ultimate compression strength (80% survival content) is 28MPa.
4th step solution method surface modification: by the aqueous solution acid-conditioning solution pH value to 5 of coupling agent (Silane coupling agent KH550), add hollow glass micro-ball again, react 8 hours at 50 DEG C, filtration, drying obtain the hollow glass micro-ball after surface modification.
Embodiment 19
The feed liquid system synthesis of the first step hollow glass micro-ball:
The 408g slurries and 545g sodium silicate solution that contain gas-phase silica 61g (are included silica 1 36g, sodium oxide 44g) include 20g ammonium borate with 67g, the solution of 20g sodium sulfate becomes water slurry liquid material, then under 30 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 20g stable dispersant polyoxyethylene again, form through colloidal mill grinding the slurries homogenized, make the solid grain size size in slurries at least be less than less than 2 microns.Wherein, gas-phase silica and water glass shared part by weight in feed liquid is 23.6%, inorganic salt shared part by weight in feed liquid is 3.9%, stable dispersant shared part by weight in feed liquid is 1%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 4.7%, sodium oxide Na
2o:3.2%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 320 DEG C, temperature out 120 DEG C, obtains the spherical precursor powder of class of 30 ~ 120 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 700 DEG C ~ 900 DEG C, the hollow glass micro-ball product that median size is 35um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 79.8% in hollow glass micro-ball thin-walled, boron oxide (weight) 2.3%, sodium oxide (weight) 17.9%.The true density of hollow glass micro-ball is 0.35g/cm
3, ultimate compression strength (80% survival content) is 8MPa.
4th step spray method surface modification: by the aqueous solution acid-conditioning solution pH value to 3 of coupling agent (Silane coupling agent KH550), atomization spray in hollow glass micro-ball surface, then carry out follow-up drying treatment obtain surface modification after hollow glass micro-ball.
Embodiment 20
The feed liquid system synthesis of the first step hollow glass micro-ball:
Slurries and the 1300g of the 2500g containing gas-phase silica 250g are included 250g boric acid, 250g SODIUMNITRATE, 150g aluminum nitrate solution become water slurry liquid material, then under 80 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 7.6g stable dispersant polyoxyethylene again, form through colloidal mill grinding the slurries homogenized, make the solid grain size size in slurries at least be less than less than 2 microns.Wherein, gas-phase silica shared part by weight in feed liquid is 6.6%, inorganic salt shared part by weight in feed liquid is 17.1%, stable dispersant shared part by weight in feed liquid is 0.2%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 27.8%, sodium oxide Na
2o:18.4%, aluminium oxide Al
2o
3: 4.2%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 320 DEG C, temperature out 120 DEG C, obtains the spherical precursor powder of class of 50 ~ 100 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 600 DEG C ~ 800 DEG C, the hollow glass micro-ball product that median size is 40um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 61.4% in hollow glass micro-ball thin-walled, boron oxide (weight) 13.9%, sodium oxide (weight) 16.5%, aluminum oxide (weight) 8.2%.The true density of hollow glass micro-ball is 0.25g/cm
3, ultimate compression strength (80% survival content) is 3MPa.
4th step spray method surface modification: by the aqueous solution acid-conditioning solution pH value to 3 of coupling agent (Silane coupling agent KH550), atomization spray in hollow glass micro-ball surface, then carry out follow-up drying treatment obtain surface modification after hollow glass micro-ball.
Embodiment 21
The feed liquid system synthesis of the first step hollow glass micro-ball:
Colloidal sol and the 700g of the 6000g containing silica gel micro mist 600g are included 100g boric acid, 200g SODIUMNITRATE, 50g nitrocalcite solution become colloidal sol, then under 80 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 26g stable dispersant polyoxyethylene again, form through colloidal mill grinding the slurries homogenized.Wherein, silica gel micro mist shared part by weight in feed liquid is 9.0%, inorganic salt shared part by weight in feed liquid is 5.2%, stable dispersant shared part by weight in feed liquid is 2%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 7.5%, sodium oxide Na
2o:10.0%, calcium oxide CaO:1.6%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 320 DEG C, temperature out 125 DEG C, obtains the spherical precursor powder of class of 50 ~ 100 microns.
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 850 DEG C ~ 1050 DEG C, the hollow glass micro-ball product that median size is 38um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 84.8% in hollow glass micro-ball thin-walled, boron oxide (weight) 3.8%, sodium oxide (weight) 9.0%, calcium oxide (weight) 2.4%.The true density of hollow glass micro-ball is 0.45g/cm
3, ultimate compression strength (80% survival content) is 45MPa.
4th step spray method surface modification: by the aqueous solution acid-conditioning solution pH value to 3 of coupling agent (Silane coupling agent KH550), atomization spray in hollow glass micro-ball surface, then carry out follow-up drying treatment obtain surface modification after hollow glass micro-ball.
Embodiment 22
The feed liquid system synthesis of the first step hollow glass micro-ball:
The slurries of the 3667g containing gas-phase silica 550g and 51g potassium silicate solution (are included silica 1 3.7g, potassium oxide 6.3g) include 40g ammonium borate with 425g, 40g sodium carbonate, 30g calcium carbonate, 20g aluminum nitrate, 20g magnesium sulfate, the solution of 20g potassium sulfate becomes water slurry liquid material, then under 30 DEG C and normal pressure, homogenizer is adopted it fully to be mixed, through reaction, add the glue 200ml of the high molecular polymer containing 5.0g stable dispersant polyoxyethylene again, the slurries homogenized are formed through sand mill grinding, the solid grain size size in slurries is made at least to be less than less than 2 microns.Wherein, gas-phase silica and potassium silicate shared part by weight in feed liquid is 14.2%, inorganic salt shared part by weight in feed liquid is 4.2%, stable dispersant shared part by weight in feed liquid is 0.12%, and the kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide B
2o
3: 3.8%, sodium oxide Na
2o:3.5%, calcium oxide CaO:2.6%, magnesium oxide MgO:0.4%, potassium oxide K
2o:1.0%, aluminium oxide Al
2o
3: 2.6%.
The spherical precursor powder synthesis of second step class: the slurries the homogenized the first step obtained are transported in atomizer moisture eliminator, atomization quick dewatering drying temperature is inlet temperature 320 DEG C, temperature out 120 DEG C, obtains the spherical precursor powder of class of 30 ~ 100 microns;
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder is entered into vitrifying gasification agglomerating plant system by an air-Sweet natural gas-powder three telescoping burning sintering device, in system, maximum glass sintering temperature is adjusted within the scope of 900 DEG C ~ 1100 DEG C, the hollow glass micro-ball product that median size is 30um can be formed, the volume its floatability of product is more than 90% (volume ratio of the solid glass microballoon namely precipitated in water and the hollow glass micro-ball of floating on water is more than 1/9), dioxide-containing silica (weight) 87.9% in hollow glass micro-ball thin-walled, boron oxide (weight) 1.9%, sodium oxide (weight) 3.2%, calcium oxide (weight) 2.8%, aluminum oxide (weight) 0.4%, magnesium oxide (weight) 1.0%, potassium oxide (weight) 2.8%.The true density of hollow glass micro-ball is 0.55g/cm
3, ultimate compression strength (80% survival content) is 50MPa.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (10)
1. a hollow glass micro-ball, is characterized in that, described hollow glass micro-ball is prepared from as follows:
The feed liquid system synthesis of the first step hollow glass micro-ball: adopt solution, colloidal sol or homodisperse aqueous slurry as feed liquid system, this feed liquid system contains SiO
2and/or containing SiO
2basic metal or the silicate solutions of alkaline-earth metal, colloidal sol or slurries material, inorganic salt material, stable dispersant and water, wherein SiO
2and/or containing SiO
2basic metal or the silicate solutions of alkaline-earth metal, colloidal sol or slurries material shared by the ratio of whole feed liquid system be 6 ~ 30% (weight), the ratio of whole feed liquid system shared by inorganic salt material is 3 ~ 25% (weight), the ratio of whole feed liquid system shared by stable dispersant is 0.1 ~ 2% (weight), and surplus is water; The feed liquid system synthesis step of hollow glass micro-ball is as follows:
According to ratio (weight) shared in feed liquid system by the SiO of 6 ~ 30%
2and/or containing SiO
2basic metal or the silicate solutions of alkaline-earth metal, colloidal sol or water slurry liquid material and 3 ~ 25% inorganic salt material be mixed with solution, colloidal sol or water slurry liquid material, then under 30 ~ 80 DEG C and normal pressure, it is fully mixed, through reaction, add the solution or colloidal sol or slurries that obtain homogeneous after 0.1 ~ 2% stable dispersant homogenizes again, make the solid grain size size in the slurries of formation guarantee at least to be less than less than 2 microns;
Second step class spherical precursor powder synthesizes: the solution the homogenized the first step obtained or colloidal sol or slurries obtain the spherical precursor powder of micron order class by atomization quick dewatering drying method;
3rd step vitrifying sintering: spherical for the micron order class of gained in second step precursor powder can be obtained by 600 ~ 1100 DEG C of vitrifying sintering processes the micron order hollow glass micro-ball that volume its floatability is greater than 90%; Made hollow glass micro-ball is that micron order inside is full of the hollow and thin-walled glass microsphere of gas, dioxide-containing silica (weight) 55 ~ 88% in thin-walled, its true density is 0.1 ~ 0.7g/cm3,80% survival content time ultimate compression strength be 1 ~ 50MPa.
2. a kind of hollow glass micro-ball according to claim 1, it is characterized in that, also comprise the 4th step surface modification: solution method: by aqueous solution acid-conditioning solution pH value to 2 ~ 5 of the aqueous solution of superpolymer or coupling agent, add hollow glass micro-ball again, reaction 0.5 ~ 8 hour at room temperature ~ 80 DEG C, filters, drying obtains the hollow glass micro-ball after surface modification; Or spray method: by the aqueous solution of coupling agent acid-conditioning solution pH value to 2 ~ 5, atomization spray in hollow glass micro-ball surface, then carry out follow-up drying treatment obtain surface modification after hollow glass micro-ball.
3. a kind of hollow glass micro-ball according to claim 1, is characterized in that, described SiO
2for gas-phase silica, precipitated silica, silicon sol, silica gel micro mist or superfine quartz sand micro mist; Described contains SiO
2basic metal or the silicate of alkaline-earth metal comprise Starso, water glass, water glass potassium, potassium silicate, lithium silicate or silicic acid quaternary amine; Described stable dispersant comprises tensio-active agent or high molecular weight water soluble polymer.
4. a kind of hollow glass micro-ball according to claim 1, it is characterized in that, described inorganic salt material is water-soluble and/or water-insoluble boron, sodium, calcium, aluminium, magnesium, the inorganic salt of potassium or lithium, comprise: boric acid, borax, ammonium borate, sodium-chlor, sodium carbonate, SODIUMNITRATE, sodium sulfate, calcium chloride, calcium carbonate, nitrocalcite, calcium hydroxide, aluminum chloride, aluminum nitrate, Tai-Ace S 150, magnesium chloride, magnesium nitrate, magnesium sulfate, salt of wormwood, saltpetre, potassium sulfate, potassium hydroxide, lithium nitrate, Quilonum Retard or hydronium(ion) Lithium Oxide 98min, kind containing above-mentioned inorganic salt material in feed liquid and content (weight percentage) are converted into oxide compound feature request according to it and are calculated as boron oxide: 3-30%, sodium oxide: 0-32%, calcium oxide: 0-15%, aluminum oxide: 0-5%, magnesium oxide: 0-5%, potassium oxide: 0-5%, Lithium Oxide 98min: 0-2%, preferably, described high molecular weight water soluble polymer is polyoxyethylene glycol, polyacrylamide, polyoxyethylene or polyvinyl alcohol.
5. a kind of hollow glass micro-ball according to claim 1, it is characterized in that, the feed liquid system of described hollow glass micro-ball also comprises ultra-low-alkali borosilicate glass system, alkaline earth borosilicate glass system, alumina silicate glass system, aluminum borate glass system, phosphate glass system or aluminum oxide, zirconium white diluted system.
6. a kind of hollow glass micro-ball according to claim 1, is characterized in that, being atomized quick dewatering drying temperature in second step is 200 ~ 400 DEG C; In 3rd step, vitrifying sintering temperature is 700 ~ 1000 DEG C.
7. a kind of hollow glass micro-ball according to claim 1, is characterized in that, being atomized quick dewatering drying equipment in second step is pneumatic conveying dryer device, spray drying device or fluidized drying equipment; Preferably, described pneumatic conveying dryer is pulse mode pneumatic dryer, ring-like pneumatic dryer or rotation flash dryer; Spray drying device is atomizer moisture eliminator, pneumatic spray drying device or press spray moisture eliminator; Fluidized drying equipment is single-layer fluidized bed moisture eliminator, spouted bed dryer or fluidized bed spray granulation moisture eliminator.
8. a kind of hollow glass micro-ball according to claim 1, is characterized in that, obtaining micron order class spherical precursor powder particle size distribution range in second step is 5 ~ 200 microns.
9. a kind of hollow glass micro-ball according to claim 1, it is characterized in that, in 3rd step, vitrifying agglomerating plant comprises: precursor powder-material conveying equipment, burner gasification vitrifying agglomerating plant, burner block and grading collecting device, preferably, described burner gasification vitrifying agglomerating plant comprises: blowing-type diffusion burner and natural induced draft formula burner; The structure of burner gasification vitrifying agglomerating plant is telescoping burning sintering device, whirlwind-type burning sintering device or Half Streaming burner.
10. a kind of hollow glass micro-ball according to any one of claim 1-9, it is characterized in that, dioxide-containing silica (weight) 55 ~ 88% in the thin-walled of described hollow glass micro-ball, boron oxide (weight) 3 ~ 30%, sodium oxide (weight) 2 ~ 32%, calcium oxide (weight) 0 ~ 15%, aluminum oxide (weight) 0 ~ 5%, magnesium oxide (weight) 0 ~ 5%, potassium oxide (weight) 0 ~ 5%, Lithium Oxide 98min (weight) 0 ~ 2%, its density is: 0.1 ~ 0.7g/cm
3.
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