CN102989581A - Method for removing radioactivity of red mud - Google Patents
Method for removing radioactivity of red mud Download PDFInfo
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- CN102989581A CN102989581A CN2012103723145A CN201210372314A CN102989581A CN 102989581 A CN102989581 A CN 102989581A CN 2012103723145 A CN2012103723145 A CN 2012103723145A CN 201210372314 A CN201210372314 A CN 201210372314A CN 102989581 A CN102989581 A CN 102989581A
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- red mud
- monazite
- slurry
- radioactivity
- flotation
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- 238000000034 method Methods 0.000 title claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 claims abstract description 26
- 229910052590 monazite Inorganic materials 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 24
- 239000011707 mineral Substances 0.000 claims abstract description 24
- 238000005188 flotation Methods 0.000 claims abstract description 20
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 19
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000007885 magnetic separation Methods 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003784 tall oil Substances 0.000 claims abstract description 6
- 230000002285 radioactive effect Effects 0.000 claims description 21
- 230000008030 elimination Effects 0.000 claims description 12
- 238000003379 elimination reaction Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000005307 ferromagnetism Effects 0.000 claims description 6
- 239000008396 flotation agent Substances 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 239000004566 building material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000004131 Bayer process Methods 0.000 description 4
- 229910001570 bauxite Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 229910052776 Thorium Inorganic materials 0.000 description 3
- 229910052770 Uranium Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000009866 aluminium metallurgy Methods 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000941 radioactive substance Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- HCWPIIXVSYCSAN-IGMARMGPSA-N Radium-226 Chemical compound [226Ra] HCWPIIXVSYCSAN-IGMARMGPSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910004369 ThO2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052585 phosphate mineral Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012857 radioactive material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- -1 this moment Chemical compound 0.000 description 1
- ZSLUVFAKFWKJRC-UHFFFAOYSA-N thorium Chemical compound [Th] ZSLUVFAKFWKJRC-UHFFFAOYSA-N 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for removing radioactivity of red mud. The method for removing the radioactivity of the red mud is characterized by comprising the following steps of: slurrying the red mud, carrying out magnetic separation on slurry, and selecting magnetic mineral materials in the slurry, wherein the magnetic mineral materials include ilmenite, iron ore and monazite; carrying out flotation on residual slurry, and selecting zircon from the treated residual slurry. According to the method, a mineral phase of the red mud is analyzed, and according to physical property differences of different minerals, through performing strong magnetic separation (greater than 6500 gausses) on the red mud slurry, the magnetic mineral materials including the iron ore, the ilmenite and the monazite in the red mud slurry are separated from other substances, and the ilmenite and the iron ore are selected through performing weak magnetic separation, so that the monazite is separated and enriched; and then slurry containing the zircon is added in a combined reagent taking tall oil as a main body so as to be subjected to floatation in a high-alkalinity (pH>12) medium, and the monazite is separated from the slurry containing the zircon and is enriched so as to lower or even eliminate the radioactivity of the red mud, and the radioactivity of slug materials meets the A-type building material standard of the national building material radioactivity standard.
Description
Technical field
The present invention relates to the radioactive method of a kind of elimination red mud, belong to red mud recovery technology field.
Background technology
Red mud is the industrial solid wastes in the aluminum oxide production process, and general every production 1 t aluminium oxide just produces 1. 0～1. 8 t red muds, has two characteristics of strong basicity and high radioactivity.According to the different process of alumina producing, red mud is divided into Bayer process and two kinds of sintering process are dissimilar.Aluminium content is high in the bauxite, adopts the Bayer process aluminium metallurgy, and the red mud that produces claims Bayer process red mud; Aluminium content is low in the bauxite, uses the sintering process aluminium metallurgy, and the red mud that produces is called red mud from sintering process.The method of disposal of red mud is mainly stacked for a long time in the stockyard at present.The construction of red mud dump can utilize the landform such as mountain valley, dell in the mountain area, stacks with dell; The deep-sea is directly inputted with pipeline in the coastal area, and natural sediment is in the seabed.Above method all will take a large amount of soils, and the chemical composition in the red mud infiltrates soil, causes the ecological environment problems such as soil alkalization, underground water pollution.The comprehensive utilization of red mud although there are many people to carry out research, such as being used for building material field as the building additive, also is useful on construction materials such as producing sulfate cement brick, ceramic tile, insulating brick, microporous calcium silicate; Suit measures to local conditions, carry out the soil according to the residing geographical conditions of aluminium manufacturer and fill and reclaim wasteland, with red mud fill stone pit, making roadbed, build He Ba, in and acid ground etc.; Utilize red mud to prepare inolrganic chemicals, water purification adsorbent etc.; Reclaim the oxides such as Al2O3, TiO2 contained in the red mud, SiO2, Na2O, CaO, and contain the metallic elements such as elements K, Mg, Ni, Zr, Sc, REE, radioactive element.But said method rests on the laboratory research stage more, all unrealized scale utilization.At present, red mud utilization rate less than 10 %, domestic accumulative total volume of cargo in storage surpasses 5,000 ten thousand t.
At present, the maximum field that can dispose red mud fully is building material industry, but high radioactivity is the difficult problem that restriction is used.There is strict demand countries in the world to the specific radioactivity of construction material.China's " the radioactive material nucleic is limited the quantity of " (GB656622001) stipulates, the specific radioactivity of natural radionuclide 226 Ra, 232 Th and 40 K satisfies internal radiation index IRa≤1. 0 and external exposure index Ir≤simultaneously at 1. 0 o'clock in the construction main body material, and its production and marketing and the scope of application are unrestricted; The specific radioactivity of natural radionuclide 226 Ra, 232 Th and 40 K satisfies simultaneously that internal radiation index IRa≤1. 0 and external exposure index Ir≤1. 3 require in the finishing material is A class finishing material; The finishing material production and marketing of A class and the scope of application are unrestricted.
The radioactive elements such as the common contained U of bauxite, Th are composed and are stored in the zircon and monazite.The zircon theoretical content is ZrO2 67. 2 %, and SiO2 32. 8 % contain 0. 5 %～4 % HfO2,0. 35 %Fe2O3 usually, the elements such as 0. 05 %～4 %CaO and a small amount of REE, Nb, Ta, Th, U.Monazite (REPO4) is the phosphate mineral that contains LREE, except containing Th, U, still contain the impurity such as ZrO2, SiO2, its chief component is: about 60 % of RE2O3, about 12 % of ThO2, UO3 and micro-Ra (0. 1 %～0. 3 %); Hardness 5. 0～5. 5, the 4 g/ cm3 of density 4. 6～5..In aluminum oxide production process, the above radioactive element of 90 % is enriched in the red mud, is the general higher basic reason of radioactivity in the red mud.In the bauxite of Guizhou output, about 0. 1 % of ree content, U, Th content＜0. 01 %, K2O＜1 %, zircon (in ZrO2) 0. 15 %, about 0. 45 % of monazite (REPO4).Containing radioactive zircon and monazite and be present in the red mud with the raw ore form in the Bayer process smelting process, is to cause highly radioactive main cause.
Summary of the invention
The object of the invention is to, provide a kind of elimination red mud radioactive method.Can environmental protection, cheaply the radioactive substance in the red mud (zircon and monazite) is separated from red mud slurry, enrichment out, reduce even eliminate the radioactive purpose of red mud to reach.
Technical scheme of the present invention.Eliminate the radioactive method of red mud, comprise the steps,
A, with red mud slurrying, slurry carries out magnetic separation, selects magnetic mineral aggregate wherein, comprises ilmenite, iron ore and monazite;
B, remaining slurry are selected zircon wherein by flotation.
The above-mentioned radioactive method of elimination red mud, among the described step a, described magnetic separation is that slurry is by the high intensity magnetic separation system of magnetic field intensity greater than 6500-6800 Gauss, select magnetic mineral aggregate wherein, comprise ilmenite, iron ore, monazite, the mineral aggregate of selecting is not more than 6500 Gausses' magnetic separation system again by magnetic field intensity, select and contain the ferromagnetism mineral aggregate, comprise iron ore, ilmenite, make monazite and contain the ferromagnetism mineral aggregate and separate, make the further enrichment of monazite.
The above-mentioned radioactive method of elimination red mud, among the described step b, described flotation is, by weight, in 1000 parts of slurries, add by 0.5-1.5 part tall oil 1-2 part waterglass, the flotation agent that 0.8-1.8 part oxidized paraffin wax soap and 0.5-1.8 part enuatrol form, in the medium of pH＞12, carry out flotation after mixing, zircon is separated.
The above-mentioned radioactive method of elimination red mud, described flotation agent also comprises 5-10 part NaOH.
The above-mentioned radioactive method of elimination red mud, the pH value of described flotation medium is 13-13.5.
The present invention is by the mineral analysis to red mud, physical difference according to different minerals, by with red mud slurry high intensity magnetic separation (greater than 6500 Gausses), with magnetic mineral aggregate wherein, comprise iron ore, ilmenite, monazite and other separating substances are out, through low intensity magnetic separation ilmenite and iron ore are selected again, so that monazite separates, enrichment out, the combination medicament of slurry adding take tall oil as main body that then will contain zircon carries out flotation in high alkalinity (pH＞12) medium, zircon is therefrom separated, enrichment, to reduce, even thoroughly eliminate the radioactivity of red mud, make the radioactivity of its slag charge reach the category-A building standard of radioactivity of building materials national standard, production and marketing and the scope of application all need not be restricted, and have carried forward vigorously the application of red mud in building material field.Through applicant test, the red mud slurries after processing according to the inventive method detects the emission ratio activity Ira of its radionuclide radium-226, thorium-232, kalium-40≤1.0, Ir≤1.0.After the elimination of the radioactivity in the red mud, magnetic separation ilmenite, iron ore, monazite out, and the mineral aggregate such as zircon, can also recycle, eat dried bleed the useful value of red mud in, not only thoroughly eliminate environmental pollution and potential safety hazard that the red mud dam brings, also alleviated the pressure that resource, environment bring, realized the unification of economic benefit, social benefit and environmental benefit.
The specific embodiment
Embodiments of the invention 1.Eliminate the radioactive method of red mud, comprise the steps,
A, with red mud slurrying, slurry carries out magnetic separation, selects magnetic mineral aggregate wherein, comprises ilmenite, iron ore and monazite;
B, remaining slurry are selected zircon wherein by flotation.
Can with the separation of the radioactive substance in the red mud, enrichment, reduce the radioactivity of red mud by said method.
Embodiments of the invention 2.Eliminate the radioactive method of red mud, concrete technology is as follows, described magnetic separation be slurry by the high intensity magnetic separation system of magnetic field intensity greater than 6500-6800 Gauss, select magnetic mineral aggregate wherein, comprise ilmenite, iron ore, monazite, the mineral aggregate of selecting is not more than 6500 Gausses' magnetic separation system again by magnetic field intensity, select and contain the ferromagnetism mineral aggregate, comprise iron ore, ilmenite, this moment, monazite can't be magneticly elected, make monazite and contain the ferromagnetism mineral aggregate and separate, make the further enrichment of monazite.Can be with the monazite enriching and recovering in the red mud, and can reduce the radioactivity of red mud.
Described flotation is by weight, to add by 0.5-1.5 part tall oil in 1000 parts of slurries, 1-2 part waterglass, 0.8-1.8 the flotation agent that part oxidized paraffin wax soap and 0.5-1.8 part enuatrol form carries out flotation after mixing in the medium of pH＞12, zircon is separated.Through applicant's test, directly add tall oil, also can select zircon, but effect is not ideal enough.The proportioning of flotation agent of the present invention, can in the high alkalinity medium, carry out flotation, and the pH value of flotation medium reaches 13-13.5, flotation effect is best, therefore, if when the red mud slurries pH of flotation is inadequate, also need to add 5-10 part NaOH, to improve the pH value of flotation medium, reach best flotation effect.Through applicant's test, the zircon flotation recovery rate in the red mud can reach more than 80%.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, any technical solution of the present invention content that do not break away from,, all still belong in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment does according to technical spirit of the present invention.
Claims (5)
1. eliminate the radioactive method of red mud for one kind, it is characterized in that: comprise the steps,
A, with red mud slurrying, slurry carries out magnetic separation, selects magnetic mineral aggregate wherein, comprises ilmenite, iron ore and monazite;
B, remaining slurry are selected zircon wherein by flotation.
2. the radioactive method of elimination red mud according to claim 1, it is characterized in that: among the described step a, described magnetic separation is that slurry is by the high intensity magnetic separation system of magnetic field intensity greater than 6500-6800 Gauss, select magnetic mineral aggregate wherein, comprise ilmenite, iron ore, monazite, the mineral aggregate of selecting is not more than 6500 Gausses' magnetic separation system again by magnetic field intensity, select and contain the ferromagnetism mineral aggregate, comprise iron ore, ilmenite, make monazite and contain the ferromagnetism mineral aggregate and separate, make the further enrichment of monazite.
3. the radioactive method of elimination red mud according to claim 1, it is characterized in that: among the described step b, described flotation is, by weight, in 1000 parts of slurries, add by 0.5-1.5 part tall oil 1-2 part waterglass, the flotation agent that 0.8-1.8 part oxidized paraffin wax soap and 0.5-1.8 part enuatrol form, in the medium of pH＞12, carry out flotation after mixing, zircon is separated.
4. the radioactive method of elimination red mud according to claim 1, it is characterized in that: described flotation agent also comprises 5-10 part NaOH.
5. the radioactive method of elimination red mud according to claim 4, it is characterized in that: the pH value of described flotation medium is 13-13.5.
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| CN2012103723145A CN102989581A (en) | 2012-09-29 | 2012-09-29 | Method for removing radioactivity of red mud |
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| CN2012103723145A CN102989581A (en) | 2012-09-29 | 2012-09-29 | Method for removing radioactivity of red mud |
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Cited By (4)
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| CN104001885A (en) * | 2014-05-06 | 2014-08-27 | 武汉振海科技有限公司 | Method for producing billet mold covering slag by means of sintering process red mud |
| CN106311715B (en) * | 2016-03-03 | 2018-10-16 | 福建洋屿环保科技股份有限公司 | A method of it is building materials to dispose red mud using permanent-magnet material and salt slurry |
| CN111438000A (en) * | 2020-04-29 | 2020-07-24 | 海南文盛新材料科技股份有限公司 | A beneficiation process for microwave pretreatment to improve monazite flotation efficiency |
| CN111530626A (en) * | 2020-04-24 | 2020-08-14 | 核工业北京化工冶金研究院 | Beneficiation method for recovering monazite from gravity concentrate of titanium dressing tailings |
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| CN111530626A (en) * | 2020-04-24 | 2020-08-14 | 核工业北京化工冶金研究院 | Beneficiation method for recovering monazite from gravity concentrate of titanium dressing tailings |
| CN111438000A (en) * | 2020-04-29 | 2020-07-24 | 海南文盛新材料科技股份有限公司 | A beneficiation process for microwave pretreatment to improve monazite flotation efficiency |
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