CN105967192B - Process and device for preparing fumed silica and recycling metal by taking industrial waste residues containing silicate as raw materials - Google Patents
Process and device for preparing fumed silica and recycling metal by taking industrial waste residues containing silicate as raw materials Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 229910021485 fumed silica Inorganic materials 0.000 title claims abstract description 30
- 239000002440 industrial waste Substances 0.000 title claims abstract description 27
- 239000002994 raw material Substances 0.000 title claims abstract description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000004064 recycling Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 title abstract description 22
- 230000008569 process Effects 0.000 title abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000010521 absorption reaction Methods 0.000 claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 19
- 150000002739 metals Chemical class 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 238000004438 BET method Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims description 148
- 238000006243 chemical reaction Methods 0.000 claims description 68
- 239000000498 cooling water Substances 0.000 claims description 42
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 34
- 238000003860 storage Methods 0.000 claims description 20
- 239000003595 mist Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 12
- 239000002912 waste gas Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- 229910052604 silicate mineral Inorganic materials 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 7
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 238000007885 magnetic separation Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005452 bending Methods 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910004298 SiO 2 Inorganic materials 0.000 abstract 1
- 239000002893 slag Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000010811 mineral waste Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
- C01B33/183—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process by oxidation or hydrolysis in the vapour phase of silicon compounds such as halides, trichlorosilane, monosilane
- C01B33/184—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process by oxidation or hydrolysis in the vapour phase of silicon compounds such as halides, trichlorosilane, monosilane by hydrolysis of tetrafluoride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Silicon Compounds (AREA)
Abstract
本发明提供了一种以含硅酸盐的工业废渣为原料低温制备气相白炭黑并回收金属的工艺，该工艺中以工业废渣等废弃物作为原料，将其与含氟酸液、盐酸以及硝酸进行反应，制备成高附加值的产物气相白炭黑并回收金属，所制得的产物中SiO2含量大于99.9％，其多点BET法测定比表面积为：350～500m2/g，达到了变废为宝的效果；上述制备工艺中所产生的酸性气体经负压水吸收罐吸收后，能够制得对应的酸液，当酸液浓缩到一定的浓度后可循环使用。同时本发明还提供了用于上述工艺中的生产装置，该生产装置所用到的零部件均为化工厂常用器具，成本低廉，能够实现大规模工业化生产。
The invention provides a process for preparing fumed silica at low temperature by using industrial waste residue containing silicate as a raw material and recovering metals. The nitric acid is reacted to prepare a high value-added product gas phase silica and the metal is recovered. The SiO 2 content in the prepared product is more than 99.9%. The specific surface area measured by the multi - point BET method is: 350 ~ 500m The effect of turning waste into treasure is achieved; the acid gas generated in the above preparation process is absorbed by the negative pressure water absorption tank, and the corresponding acid solution can be prepared, and the acid solution can be recycled after being concentrated to a certain concentration. At the same time, the present invention also provides a production device used in the above-mentioned process. The components used in the production device are all common appliances in chemical plants, and the cost is low, and large-scale industrial production can be realized.
Description
Technical Field
The invention relates to a process method and a device for preparing fumed silica and recovering metals by taking industrial waste residues containing silicate as raw materials, belonging to the technical field of chemical purification and environmental protection.
Background
Since the innovation is open, China makes great progress in science and technology and develops the economy rapidly; the method is particularly and rapidly developed in the aspects of mining, metal smelting, coal-fired power plants, chemical industry, building materials and the like; meanwhile, a large amount of industrial waste residues are discharged in the industrial development process: such as: copper slag, magnesium slag, nickel slag, aluminum sulfate slag, lithium slag, blast furnace slag, iron alloy slag, lead-zinc slag, granulated circuit phosphorus slag and the like; also non-metallic ore waste residues: such as kaolin, feldspar, talc, pyrophyllite, bentonite, attapulgite, palygorskite, serpentine, wollastonite and other mineral waste residues; the main components of the waste residues are ferric oxide, silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, potassium oxide, sodium oxide and non-ferrous metals such as gold, silver, copper and the like. According to the data provided by the national statistical department: in 2004, the industrial waste residue is 12 hundred million tons, and in 2009, 20 hundred million tons of … … are broken through; if the industrial waste residues are not utilized, on one hand: the large amount of stockpiling not only occupies a large amount of land, but also causes serious air pollution, soil pollution and water resource pollution, harms the natural environment and human health, and becomes a public nuisance in the social development process. On the other hand, the industrial waste residue is a secondary resource, has great utilization value, and if the industrial waste residue is subjected to harmless and resource treatment, the secondary resource is scientifically, reasonably and efficiently utilized, so that the method has very important practical significance for implementing energy conservation and emission reduction, environmental protection and harmonious development of people and nature in the current society.
The raw materials for preparing the white carbon black by the vapor phase method are silicon tetrachloride, oxygen (or air) and hydrogen which are reacted at high temperature. The chemical reaction formula is as follows: SiCl4+2H2+O2-＞SiO2+4HCl, silicon tetrachloride is gasified at high temperature (flame temperature is 1000-1800 ℃), and then is subjected to gas phase hydrolysis with a certain amount of hydrogen and oxygen (or air) at high temperature of about 1800 ℃; at the moment, the generated fumed silica particles are extremely fine and form aerosol with gas, so that the aerosol is not easy to trap, and therefore the fumed silica particles are firstly gathered into larger particles in a collector, then the larger particles are collected by a cyclone separator and then sent into a deacidification furnace, and the fumed silica is blown by nitrogen-containing air until the pH value is 4-6, so that the finished product is obtained. The method is adopted by most of the enterprises producing the fumed silica in China at present, and is also a universal international production method of the fumed silica. China also has enterprises to produce fumed silica by adopting methyltrichlorosilane and successfully finishes industrialized production. The existing production process of fumed silica not only has a high-temperature process, but also uses hydrogen and oxygen which are very dangerous, flammable and explosive, and the operating environment of workers is relatively hard in the production process; the requirement on the safety coefficient is high. Relevant data and Chinese patent documents are consulted, and no relevant report of producing the fumed silica by using other raw materials is found.
If the industrial waste residue can be processed and utilized for the second time, and the industrial waste residue is combined with the preparation of the fumed silica to be used for preparing the fumed silica product, the two technical problems in the field can be solved, and the preparation method has obvious progress.
Disclosure of Invention
The invention provides a production process method and a device for preparing fumed silica and recovering metal by taking industrial waste residues containing silicate as raw materials; the invention successfully avoids the technical processes of using hydrogen and oxygen and carrying out high-temperature hydrolysis in the conventional fumed silica process, also solves the problem that the conventional industrial waste residue cannot be efficiently utilized, and simultaneously provides a novel process technology and a production device for producing fumed silica products at normal temperature and normal pressure.
The technical scheme adopted for realizing the above purpose of the invention is as follows:
a process for preparing fumed silica by taking industrial waste residues as raw materials is characterized by comprising the following steps: (1) mixing the fluorine-containing acid solution with nitric acid to prepare a mixed acid solution for later use; grinding the industrial waste residue to the fineness of below 200 meshes, magnetically separating to remove iron, concentrating and dehydrating the slurry after magnetic separation and gravity separation to obtain silicate mineral powder for analyzing SiO of the silicate mineral powder2、Al2O3、CaO、MgO、K2O、Na2The content of O is reserved; if the content of alkali metal or alkaline earth metal is high, dissolving the mixture by concentrated hydrochloric acid, filtering, washing filter residue, and dehydrating for later use; the filtrate is separately treated;
(2) putting the mixed acid liquid into a reaction kettle, starting a stirring device of the reaction kettle and a waste gas absorption device in a reaction system, and putting the material in the step (1) into the reaction kettle;
(3) controlling the reaction temperature in the reaction kettle to be 75-85 ℃, reacting hydrofluoric acid or fluosilicic acid in the mixed acid liquid with silicon dioxide in industrial waste residues to generate silicon tetrafluoride gas, and carrying the silicon tetrafluoride gas, nitric acid gas volatilized from the mixed acid liquid and water vapor into the cooling kettle under negative pressure;
(4) controlling the cooling temperature in the cooling kettle to be 10-40 ℃, and reacting the mixed gas in the cooling kettle to obtain HF and NO2Is taken out from the cooling kettle by negative pressure and is absorbed by water to generate hydrofluoric acid, nitric acid and SiO which can be used repeatedly2·nH2O is condensed and adsorbed on a cooling device in a cooling kettle, and SiO in the cooling kettle is collected2·nH2O；
(5) Collecting the SiO2·nH2Preheating O in vacuum heater under negative pressure to remove residual HF and NO2Then drying, and obtaining the gas-phase white carbon black product after drying, wherein SiO in the product2The content is more than 99.9 percent, and the specific surface area is not less than 350m by the multi-point BET method2/g；
(6) Decomposing silicon dioxide and aluminum oxide in silicate mineral powder by using a fluorine-containing acid solution in a reaction kettle; the nitric acid decomposes the residual metal in the material, and the decomposed metal is left in the mixed acid solution in the form of ions and salt; filtering after the reaction of the materials in the reaction kettle is finished, and separating out AlF in filter residue3(ii) a Then sending the filtrate into an evaporator to be evaporated to dryness, absorbing acid mist gas generated in the evaporation process into a certain concentration through water and then utilizing the acid mist gas; then a metal salt mixture can be obtained, and various metals are separated through a displacement reaction.
The mass concentration or volume concentration of the hydrofluoric acid is 2-30%, the mass concentration or volume concentration of the fluosilicic acid is 10-30%, and the mass concentration or volume concentration of the nitric acid is 2-40%.
And (4) absorbing the acid mist gas generated in the evaporation in the step (6) by using a water absorption tank to obtain acid liquor, returning the acid liquor to a workshop for reuse after the acid liquor reaches a certain concentration, and neutralizing the unabsorbed tail gas by using an acid mist absorption tower and then emptying the tail gas.
The invention also provides a device used in the process, which comprises a hot air feeding system, a chemical reaction system, a cooling system and a waste gas absorption system, wherein the hot air feeding system is used for storing compressed air, heating the air and then feeding the air into a synthesis system; the synthesis system consists of an acid liquor storage tank, a storage bin and a reaction kettle, wherein the bottoms of the acid liquor storage tank and the storage bin are communicated with the reaction kettle through a pipeline, a stirring device is arranged in the reaction kettle, the lining of the reaction kettle is made of a temperature-resistant, acid-resistant and wear-resistant material, an annular round pipe is arranged above the bottom of the reaction kettle, air holes or air vent pipes are uniformly distributed on the round pipe, more than one vertical pipe communicated with the annular round pipe is arranged in the reaction kettle, and the top end of the vertical pipe is communicated with a hot air feeding system through a pipe valve on a kettle cover of the reaction kettle; the upper end and the lower end of the tube bundle are respectively connected with cold and hot media outside the kettle wall through a valve, and the heating or cooling is provided for a reaction system in the kettle by introducing the cold and hot media into the capillary tubes in the tube bundle.
The cooling system is formed by connecting a primary cooling kettle and a secondary cooling kettle in series; the device comprises a primary cooling kettle, a reaction kettle, a secondary cooling kettle, a cooling device, a discharge valve, a pipeline, a pressure sensor and a control system, wherein the primary cooling kettle is connected with the reaction kettle, the pipeline which is connected with the primary cooling kettle and extends into the center of the bottom of the primary cooling kettle is arranged on a kettle cover of the reaction kettle, the cooling device is arranged inside the primary cooling kettle, the discharge valve is arranged at the bottom of the secondary cooling kettle; the kettle cover of the secondary cooling kettle is provided with a pipeline connected with a waste gas absorption system, the waste gas absorption system consists of more than one negative pressure water absorption tank and an acid mist absorption device, and the top of the negative pressure water absorption tank is provided with a pipeline and is connected with an induced draft fan in the acid mist absorption device through the pipeline.
The hot air feeding system comprises an air compressor, an air storage tank, an air heater and a pipeline, wherein the air compressor, the air storage tank and the air heater are connected through the pipeline, and the pipeline is further provided with a valve and an instrument.
The reactor is characterized in that vent pipes with diameters of 10-20 mm and different orientations are uniformly distributed on the round pipe, the distance between every two adjacent vent pipes is 50-150 mm, the included angle between the extending directions of the adjacent vent pipes is 60-120 degrees, two vertical pipes are arranged in the reactor, and the two vertical pipes are respectively connected to the left end and the right end of the round pipe.
The cooling device of the primary cooling kettle consists of a rotating shaft and a cooling disc, the rotating shaft is a hollow round pipe wrapped with polytetrafluoroethylene, the top end of the rotating shaft extends out of the kettle cover of the primary cooling kettle, a cooling water pipe A from top to bottom is arranged in the rotating shaft, the top of the cooling water pipe A is a water inlet end, and the water inlet end is connected with a cooling water source; cooling discs are uniformly distributed on the rotating shaft, the cooling discs are fixedly arranged on the rotating shaft by taking the rotating shaft as the circle center and rotate along with the rotating shaft, the cooling discs are of a hollow structure, cooling water pipes B which are distributed in a spiral shape are arranged inside all the cooling discs, the cooling water pipes B in the cooling discs which are adjacent up and down are connected end to end, the water inlet end of the cooling water pipe B in the bottommost cooling disc is communicated with the bottom end of the cooling water pipe A, the water outlet end of the cooling water pipe B in the topmost cooling disc is communicated with a hollow circular pipe, and cooling water discharged from the cooling water pipe B overflows from the top end of the rotating shaft; the cooling disc is uniformly distributed with vertical vent holes, and the vent holes on the cooling disc adjacent to each other are staggered.
The diameter of each vent hole is 10-20 mm, and the center distance between every two adjacent vent holes is 20-30 mm.
The kettle cover of the one-level cooling kettle is provided with a vacuum meter and a manhole convenient to overhaul, and the kettle cover of the one-level cooling kettle is also provided with a compressed air blowing device which is connected with a compressed gas source.
The cooling device in the secondary cooling kettle is of a multi-layer fin structure, a cooling water inlet and a cooling water outlet are formed in the kettle wall of the secondary cooling kettle, the cooling water inlet is communicated with a water inlet of the fin at the lowest layer, cooling water flows in from the fin at the lowest layer, the fins are of a continuous bending structure, the end parts of the adjacent upper and lower layers of fins are communicated, and the cooling water outlet is communicated with a water outlet of the fin at the uppermost layer; a compressed air blowing device is arranged on a kettle cover of the secondary cooling kettle and is connected with a compressed gas source, a vacuum meter is arranged on the kettle cover of the secondary cooling kettle, and manholes convenient to overhaul are arranged at the bottom of the kettle cover and the kettle.
The negative pressure water absorption tanks are arranged in two, and the two negative pressure water absorption tanks are connected in series or in parallel.
Compared with the prior art, the technical scheme provided by the invention has the following advantages: 1. the invention takes industrial waste residue and other wastes as raw materials to prepare the high value-added product fumed silica, and SiO in the prepared product2The content is more than 99.9 percent, and the specific surface area is not less than 350m by the multi-point BET method2The volume per gram is changed into the valuable. 2. The preparation process provided by the invention belongs to a brand new process idea, and overcomes the defects of high-temperature working procedures, use of dangerous, flammable and explosive hydrogen and oxygen and the like in the existing preparation process of the fumed silica. The production process provided by the invention can be used for preparing the nano-silver/nano-silver material at normal temperature and normal pressure. 3. The acid gas generated in the preparation process can be absorbed by the negative pressure water absorption tank to prepare corresponding acid liquid, and the acid liquid can be recycled after being concentrated to a certain concentration, so that the cost in production can be greatly saved, and the problem of waste water treatment in an environment-friendly manner can be solved. 4. The production device provided by the invention can realize large-scale industrial production, and the used parts are all common appliances of chemical plants, so that the cost is low. 5. The invention can recover high-price metal in the industrial waste residue, and has great economic benefit.
Drawings
FIG. 1 is a schematic view of the overall structure of a manufacturing apparatus according to the present invention;
FIG. 2 is a schematic structural diagram of a cooling disc in a primary cooling kettle;
FIG. 3 is a schematic structural view of fins in a secondary cooling kettle;
in the figure: 1-acid liquor storage tank, 2-stock bin, 3-reaction kettle, 4-stirring device, 5-round pipe, 6-vertical pipe, 7-primary cooling kettle, 8-secondary cooling kettle, 9-discharge valve, 10-negative pressure water absorption tank, 11-acid mist absorption device, 12-air compressor, 13-air storage tank, 14-air heater, 15-rotating shaft, 16-cooling disc, 17-cooling water pipe A, 18-vent hole and 19-fin.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and specific embodiments, but the scope of the present invention is not limited to the following embodiments.
The structure of the preparation device provided in this embodiment is as shown in fig. 1, and the device includes a hot air feeding system, a synthesis system, a cooling system, and an exhaust gas absorption system, where the hot air feeding system is used to store compressed air and heat the air and then feed the air into the synthesis system, the hot air feeding system includes an air compressor 12, an air storage tank 13, an air heater 14, and a pipe, where the air compressor 12, the air storage tank 13, and the air heater 14 are connected by the pipe, and the pipe is further provided with a valve and a meter.
The chemical reaction system comprises an acid liquor storage tank 1, a storage bin 2 and a reaction kettle 3, wherein the bottoms of the acid liquor storage tank 1 and the storage bin 2 are communicated with the reaction kettle 3 through a pipeline, a stirring device 4 is arranged in the reaction kettle 3, and the lining of the reaction kettle is made of temperature-resistant, acid-resistant and wear-resistant materials, such as silicon carbide, fluorine materials, graphite materials and the like. Department about 200mm in the top of 3 bottoms of reation kettle is equipped with an annular pipe 5, the diameter of pipe is 100 ~ 200mm, pipe 5 on evenly distributed have the diameter be 10 ~ 20mm and towards different permeability cell, the interval between the adjacent permeability cell is 50 ~ 150mm, and the contained angle between the direction of stretching out of adjacent permeability cell is 60 ~ 120. Two vertical pipes 6 communicated with an annular round pipe are arranged in the reaction kettle, the two vertical pipes 6 are respectively connected to the left end and the right end of the round pipe 5, and the top ends of the vertical pipes 6 are communicated with a hot air feeding system through pipe valves on a kettle cover of the reaction kettle. The kettle wall in the reaction kettle is provided with a spiral hook for supporting a polytetrafluoroethylene capillary tube bundle used for heating or cooling in the kettle.
The cooling system is formed by connecting a primary cooling kettle 7 and a secondary cooling kettle 8 in series; the primary cooling kettle 7 is connected with the reaction kettle 3, a pipeline which is connected with the primary cooling kettle 7 and extends into the center of the bottom of the primary cooling kettle is arranged on a kettle cover of the reaction kettle 3, a cooling device is arranged inside the primary cooling kettle 7, the cooling device of the primary cooling kettle consists of a rotating shaft 15 and a cooling disc 16, the rotating shaft 15 is a hollow round pipe wrapped with polytetrafluoroethylene, the top end of the rotating shaft extends out of the kettle cover of the primary cooling kettle, a cooling water pipe A17 from top to bottom is arranged in the rotating shaft, the top of the cooling water pipe A is a water inlet end, and the water inlet end is connected with a cooling water source; cooling discs 16 are uniformly distributed on the rotating shaft 15. The structure of cooling disc is as shown in fig. 2, cooling disc 16 uses pivot 15 to fix in the pivot as the installation of centre of a circle to rotatory along with the pivot, the cooling disc is hollow structure, and the inside of all cooling discs all is provided with and is the condenser tube B that spirals the form and distribute, and condenser tube B end to end in the adjacent cooling disc about and, and condenser tube B's in the cooling disc of bottommost intake end and condenser tube A's bottom is linked together, and condenser tube B's in the cooling disc of topmost water outlet end accesss to hollow pipe, and the cooling water of exhaust in the condenser tube B spills over by the top of pivot. The cooling disc is uniformly distributed with vertical vent holes 18, and the vent holes on the upper and lower adjacent cooling discs are staggered with each other to ensure the cooling effect of the gas. The diameter of each vent hole is 10-20 mm, and the center distance between every two adjacent vent holes is 20-30 mm.
The kettle cover of the one-level cooling kettle is provided with a vacuum meter and a manhole convenient to overhaul, and the kettle cover of the one-level cooling kettle is also provided with a compressed air blowing device which is connected with a compressed gas source. A pipeline which is connected with the second-stage cooling kettle 8 and extends into the center of the bottom of the second-stage cooling kettle 8 is arranged on the kettle cover of the first-stage cooling kettle 7. The bottom of the first-stage cooling kettle is provided with a discharge valve 9.
The inside of second grade cooling cauldron 8 be provided with cooling device, second grade cooling cauldron in cooling device be multilayer fin structure, be provided with cooling water inlet and cooling water outlet on second grade cooling cauldron 8's the cauldron wall, the cooling water inlet is linked together with the water inlet of lower floor's fin, cooling water flows in by the fin of lower floor, fin 19 is continuous bending structure, its structure is shown in fig. 3. The end parts of the adjacent upper and lower layers of fins are communicated, the cooling water outlet is communicated with the water outlet of the uppermost layer of fins, and the cooling water enters from the lowermost layer of fins and flows out from the uppermost layer of fins. And a compressed air blowing device is arranged on the kettle cover of the secondary cooling kettle and is connected with a compressed gas source, and compressed air is used for blowing during discharging. The kettle cover of the secondary cooling kettle is provided with a vacuum meter, and the kettle cover and the kettle bottom are provided with manholes convenient to overhaul. A discharge valve 9 is arranged at the bottom of the secondary cooling kettle; and a pipeline connected with the waste gas absorption system is arranged on the kettle cover of the secondary cooling kettle 8.
The waste gas absorption system consists of two negative pressure water absorption tanks 10 and an acid mist absorption device 11, and the two negative pressure water absorption tanks are connected in series or in parallel. The top of the negative pressure water absorption tank is provided with a pipeline and is connected with a draught fan in the acid mist absorption device through the pipeline. The acid mist absorbed by the secondary water absorption tank is neutralized with the fog drops of the liquid alkali solution in the acid mist absorption device and then discharged into the air, and when the acid liquid in the negative pressure water absorption tank reaches a certain concentration, the acid liquid is sent to a workshop for recycling.
The detailed preparation process of the invention is explained in detail by taking industrial waste residue produced by certain mining company in Hubei as an example, and the content of each component in the industrial waste residue is analyzed as follows: SiO 22：30.73％；Al2O3：1.32％，Fe2O3：5.95％；CaO：50.65％；K2O：0.08％；MgO：11.30％；SO3：0.10％；Na2O: 0.10 percent. The specific production steps are as follows:
(1) mixing one or two of hydrofluoric acid and fluosilicic acid with nitric acid to prepare mixed acid liquid, wherein the hydrofluoric acid, the fluosilicic acid and the nitric acid are all in industrial grade; or industrial by-products can be adopted. Preferably, the mass concentration or volume concentration of the hydrofluoric acid is 2-30%, the mass concentration or volume concentration of the fluosilicic acid is 10-30%, and the mass concentration or volume concentration of the nitric acid is 2-40%.
Grinding the industrial waste residue to the fineness of below 200 meshes, removing iron by magnetic separation, concentrating and dehydrating slurry subjected to magnetic separation and gravity separation to obtain silicate mineral powder for later use, wherein the silicate mineral powder is optimally used after being dried, but the corresponding cost is increased.
(2) And putting the mixed acid liquid into the reaction kettle, starting a stirring device of the reaction kettle and a waste gas absorption device in the reaction system, and slowly putting the silicate mineral powder into the reaction kettle.
(3) And if the added mixed acid liquid contains hydrofluoric acid, because the reaction process of the hydrofluoric acid and the silicon dioxide is a heat release process, a cooling water valve outside the reaction kettle needs to be opened to maintain the reaction temperature at 75-85 ℃. If the added mixed acid liquid does not contain hydrofluoric acid but contains fluosilicic acid, a steam valve of a jacket of the reaction kettle and a heat source valve arranged on the kettle outer wall of a spiral tetrafluoro capillary tube bundle arranged on the inner wall of the kettle are required to be opened to slowly heat the reaction kettle. And reacting hydrofluoric acid or fluosilicic acid in the mixed acid liquid with silicon dioxide in the industrial waste residue to generate silicon tetrafluoride gas, dissolving part of the gas in water in a reaction system to form fluosilicic acid, continuously dissolving the silicon dioxide in the industrial waste residue, and bringing the other part of the overflowed silicon tetrafluoride gas, the volatilized nitric acid gas and water vapor into the cooling kettle under negative pressure.
(4) Controlling the cooling temperature in the cooling kettle to be 10-40 ℃, and reacting the mixed gas in the cooling kettle to generate HF and NO2、SiO2·nH2O。
Wherein HF and NO2Overflowing from the first-stage cooling kettle and the second-stage cooling kettle, entering a waste gas absorption system and being absorbed by water to generate hydrofluoric acid and nitric acid which can be reused, wherein the hydrofluoric acid and the nitric acid can be recycled after being concentrated to a certain concentration; thus greatly saving the cost in production and solving the problem of environmental protection wastewater treatment.
And SiO2·nH2O is slowly condensed and adsorbed on a cooling disc in a primary cooling kettle, condensed on the cooling disc from the beginning, slowly and naturally crystallized to form crystal grains which are glittering and translucent, and gathered together like roes, so that the cooling kettle is very attractive, when the cooling disc of the primary cooling kettle is gathered to a certain amount, a rotating shaft device is started, the rotating shaft drives the cooling disc to rotate, materials are thrown to the kettle wall under the action of centrifugal force, and then are blown to the bottom of the primary cooling kettle by compressed air and sent to a drying process through a discharge valve at the bottom; after the materials in the first-stage cooling kettle are treated, the second-stage cooling kettle directly opens the compressed air valve, directly blows the condensed materials to the bottom of the kettle and then is sent through the discharge valve at the bottomA drying process is carried out;
(5) the material contains water and is acidic, and the volatility of hydrofluoric acid, silicon tetrafluoride and nitric acid is extremely strong, so that the collected SiO is firstly dried2·nH2Preheating O in vacuum heater under negative pressure to remove residual HF and NO2Then drying, and obtaining the gas-phase white carbon black product after drying, wherein SiO in the product2The content is more than 99.9 percent, and the specific surface area is not less than 350m by the multi-point BET method2/g。
(6) And in the acid solution reaction process: hydrofluoric acid and fluosilicic acid decompose silicon dioxide and aluminum oxide in silicate mineral powder; the nitric acid decomposes other metals and alkali metals in the material; nitric acid mainly plays an oxidizing role in the process. The decomposed metal is left in the acid solution as ions and corresponding salt; after the reaction is finished and the hot reaction product is filtered, the filter residue comprises the following main components: AlF3、TiO2Dissolving the titanium ore in the filter residue by concentrated sulfuric acid to prepare a titanium dioxide raw material; finally AlF is separated3Producing a product; the filtrate is sent into an evaporator to be evaporated and evaporated to dryness while the filtrate is hot, and a high-purity metal salt (rare earth metal) mixture can be obtained; and analyzing the content of various valuable metal elements in the mixture, and separating and extracting various metals by means of displacement, neutralization, extraction, recrystallization and the like according to the analysis result: such as gold, silver, copper, rare earth elements, etc.; and the acid mist gas generated during evaporation is absorbed by a water absorption tank for more than two stages to be changed into acid liquor, when the acid liquor reaches a certain concentration, the acid liquor returns to a workshop for reuse, and the unabsorbed tail gas is neutralized by an acid mist absorption tower and then is emptied.
Claims (9)
1. A process for preparing fumed silica and recovering metals by taking silicate-containing industrial waste residues as raw materials is characterized by comprising the following devices:
the device comprises a hot air feeding system, a chemical reaction system, a cooling system and a waste gas absorption system, wherein the hot air feeding system is used for storing compressed air, heating the air and then feeding the air into the chemical reaction system; the chemical reaction system consists of an acid liquor storage tank, a storage bin and a reaction kettle, wherein the bottoms of the acid liquor storage tank and the storage bin are communicated with the reaction kettle through a pipeline, a stirring device is arranged in the reaction kettle, the lining of the reaction kettle is made of a temperature-resistant, acid-resistant and wear-resistant material, an annular round pipe is arranged above the bottom of the reaction kettle, air holes or air vent pipes are uniformly distributed on the round pipe, more than one vertical pipe communicated with the annular round pipe is arranged in the reaction kettle, and the top end of the vertical pipe is communicated with a hot air feeding system through a pipe valve on a kettle cover of the reaction kettle; the upper end and the lower end of the tube bundle are respectively connected with a cold and hot medium outside the kettle wall through a valve, and the heating or cooling is provided for a reaction system in the kettle by introducing the cold and hot medium into the capillary tubes in the tube bundle;
the cooling system is formed by connecting a primary cooling kettle and a secondary cooling kettle in series; the device comprises a primary cooling kettle, a reaction kettle, a secondary cooling kettle, a cooling device, a discharge valve, a pipeline, a pressure sensor and a control system, wherein the primary cooling kettle is connected with the reaction kettle, the pipeline which is connected with the primary cooling kettle and extends into the center of the bottom of the primary cooling kettle is arranged on a kettle cover of the reaction kettle, the cooling device is arranged inside the primary cooling kettle, the discharge valve is arranged at the bottom of the secondary cooling kettle; a pipeline connected with a waste gas absorption system is arranged on a kettle cover of the secondary cooling kettle, the waste gas absorption system consists of more than one negative pressure water absorption tank and an acid mist absorption device, and the top of the negative pressure water absorption tank is provided with a pipeline and is connected with an induced draft fan in the acid mist absorption device through the pipeline;
the process for preparing the fumed silica and recycling the metal by adopting the device and taking the silicate-containing industrial waste residues as the raw materials comprises the following steps: (1) mixing the fluorine-containing acid solution with nitric acid to prepare a mixed acid solution for later use; grinding the industrial waste residue to the fineness of below 200 meshes, magnetically separating to remove iron, concentrating and dehydrating the slurry after magnetic separation and gravity separation to obtain silicate mineral powder for analyzing SiO of the silicate mineral powder2、Al2O3、CaO、MgO、K2O、Na2The content of O is reserved; if the content of alkali metal or alkaline earth metal is high, dissolving the mixture by concentrated hydrochloric acid, filtering, washing filter residue, and dehydrating for later use; the filtrate is separately treated;
(2) putting the mixed acid liquid into a reaction kettle, starting a stirring device of the reaction kettle and a waste gas absorption device in a reaction system, and putting the material in the step (1) into the reaction kettle;
(3) controlling the reaction temperature in the reaction kettle to be 75-85 ℃, reacting hydrofluoric acid or fluosilicic acid in the mixed acid liquid with silicon dioxide in industrial waste residues to generate silicon tetrafluoride gas, and carrying the silicon tetrafluoride gas, acid gas volatilized from the mixed acid liquid and water vapor into the cooling kettle under negative pressure;
(4) controlling the cooling temperature in the cooling kettle to be 10-40 ℃, and reacting the mixed gas in the cooling kettle, wherein HF and NO are reacted2Is taken out from the cooling kettle by negative pressure and is absorbed by water to generate hydrofluoric acid, nitric acid and SiO which can be used repeatedly2·nH2O is condensed and adsorbed on a cooling device in a cooling kettle, and SiO in the cooling kettle is collected2·nH2O；
(5) Collecting the SiO2·nH2Preheating O in vacuum heater under negative pressure to remove residual HF and NO2Then drying, and obtaining the gas-phase white carbon black product after drying, wherein SiO in the product2The content is more than 99.9 percent, and the specific surface area is not less than 350m by the multi-point BET method2/g；
(6) Decomposing silicon dioxide and aluminum oxide in silicate mineral powder by using a fluorine-containing acid solution in a reaction kettle; the nitric acid decomposes the residual metal in the material, and the decomposed metal is left in the mixed acid solution in the form of ions and salt; filtering after the reaction of the materials in the reaction kettle is finished, and separating out AlF in filter residue3(ii) a Then sending the filtrate into an evaporator to be evaporated to dryness to obtain a high-purity metal salt mixture, and respectively separating and extracting each metal in the metal mixture to obtain different high-purity metals.
2. The process for preparing fumed silica and recovering metals according to claim 1, characterized in that: the mass concentration or volume concentration of the hydrofluoric acid is 2-30%, the mass concentration or volume concentration of the fluosilicic acid is 10-30%, and the mass concentration or volume concentration of the nitric acid is 2-40%.
3. The process for preparing fumed silica and recovering metals according to claim 1, characterized in that: and (4) absorbing the acid mist gas generated in the evaporation in the step (6) by using a water absorption tank to obtain acid liquor, returning the acid liquor to a workshop for reuse after the acid liquor reaches a certain concentration, and neutralizing the unabsorbed tail gas by using an acid mist absorption tower and then emptying the tail gas.
4. The process for preparing fumed silica and recovering metals according to claim 1, characterized in that: the hot air feeding system comprises an air compressor, an air storage tank, an air heater and a pipeline, wherein the air compressor, the air storage tank and the air heater are connected through the pipeline, and the pipeline is further provided with a valve and an instrument.
5. The process for preparing fumed silica and recovering metals according to claim 1, characterized in that: the reactor is characterized in that vent pipes with diameters of 10-20 mm and different orientations are uniformly distributed on the round pipe, the distance between every two adjacent vent pipes is 50-150 mm, the included angle between the extending directions of the adjacent vent pipes is 60-120 degrees, two vertical pipes are arranged in the reactor, and the two vertical pipes are respectively connected to the left end and the right end of the round pipe.
6. The process for preparing fumed silica and recovering metals according to claim 1, characterized by: the cooling device of the primary cooling kettle consists of a rotating shaft and a cooling disc, the rotating shaft is a hollow round pipe wrapped with polytetrafluoroethylene, the top end of the rotating shaft extends out of the kettle cover of the primary cooling kettle, a cooling water pipe A from top to bottom is arranged in the rotating shaft, the top of the cooling water pipe A is a water inlet end, and the water inlet end is connected with a cooling water source; cooling discs are uniformly distributed on the rotating shaft, the cooling discs are fixedly arranged on the rotating shaft by taking the rotating shaft as the circle center and rotate along with the rotating shaft, the cooling discs are of a hollow structure, cooling water pipes B which are distributed in a spiral shape are arranged inside all the cooling discs, the cooling water pipes B in the cooling discs which are adjacent up and down are connected end to end, the water inlet end of the cooling water pipe B in the bottommost cooling disc is communicated with the bottom end of the cooling water pipe A, the water outlet end of the cooling water pipe B in the topmost cooling disc is communicated with a hollow circular pipe, and cooling water discharged from the cooling water pipe B overflows from the top end of the rotating shaft; the cooling disc is uniformly distributed with vertical vent holes, and the vent holes on the cooling disc adjacent to each other are staggered.
7. The process for preparing fumed silica and recovering metals according to claim 6, characterized by: the diameter of each vent hole is 10-20 mm, and the center distance between every two adjacent vent holes is 20-30 mm.
8. The process for preparing fumed silica and recovering metals according to claim 6, characterized by: the kettle cover of the one-level cooling kettle is provided with a vacuum meter and a manhole convenient to overhaul, and the kettle cover of the one-level cooling kettle is also provided with a compressed air blowing device which is connected with a compressed gas source.
9. The process for preparing fumed silica and recovering metals according to claim 1, characterized in that: the cooling device in the secondary cooling kettle is of a multi-layer fin structure, a cooling water inlet and a cooling water outlet are formed in the kettle wall of the secondary cooling kettle, the cooling water inlet is communicated with a water inlet of the fin at the lowest layer, cooling water flows in from the fin at the lowest layer, the fins are of a continuous bending structure, the end parts of the adjacent upper and lower layers of fins are communicated, and the cooling water outlet is communicated with a water outlet of the fin at the uppermost layer; a compressed air blowing device is arranged on a kettle cover of the secondary cooling kettle and is connected with a compressed gas source, a vacuum meter is arranged on the kettle cover of the secondary cooling kettle, and manholes convenient to overhaul are arranged at the bottom of the kettle cover and the kettle.
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| CN101774587A (en) * | 2010-02-11 | 2010-07-14 | 浙江中宁硅业有限公司 | Method for preparing silicon tetrafluoride by quartz sand |
| US20120082610A1 (en) * | 2010-10-02 | 2012-04-05 | Channon Matthew J | Fluorspar/Iodide process for reduction,purificatioin, and crystallization of silicon |
| CN102351150B (en) * | 2011-07-11 | 2013-02-27 | 多氟多化工股份有限公司 | Method for preparing hydrogen fluoride and coproducing white carbon black with silicon tetrafluoride |
| CN105110344B (en) * | 2015-08-19 | 2017-02-01 | 六盘水师范学院 | Method and apparatus for preparing fumed silica from coal gangue |
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