CN115259186A - Magnesium sulfate solution refined from asbestos tailings and preparation method thereof - Google Patents
Magnesium sulfate solution refined from asbestos tailings and preparation method thereof Download PDFInfo
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- CN115259186A CN115259186A CN202211021837.5A CN202211021837A CN115259186A CN 115259186 A CN115259186 A CN 115259186A CN 202211021837 A CN202211021837 A CN 202211021837A CN 115259186 A CN115259186 A CN 115259186A
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- magnesium sulfate
- sulfate solution
- asbestos tailings
- reaction
- leaching
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 title claims abstract description 106
- 239000010425 asbestos Substances 0.000 title claims abstract description 74
- 229910052895 riebeckite Inorganic materials 0.000 title claims abstract description 74
- 229910052943 magnesium sulfate Inorganic materials 0.000 title claims abstract description 53
- 235000019341 magnesium sulphate Nutrition 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000002386 leaching Methods 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000000047 product Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 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 claims description 16
- 238000007670 refining Methods 0.000 claims description 16
- 239000000395 magnesium oxide Substances 0.000 claims description 14
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000292 calcium oxide Substances 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 13
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 235000010755 mineral Nutrition 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052839 forsterite Inorganic materials 0.000 claims description 6
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- 229910052595 hematite Inorganic materials 0.000 claims description 5
- 239000011019 hematite Substances 0.000 claims description 5
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052599 brucite Inorganic materials 0.000 claims description 3
- 229910001919 chlorite Inorganic materials 0.000 claims description 3
- 229910052619 chlorite group Inorganic materials 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052742 iron Inorganic materials 0.000 abstract description 16
- -1 iron ions Chemical class 0.000 abstract description 14
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 23
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 14
- 229910001425 magnesium ion Inorganic materials 0.000 description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000011085 pressure filtration Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a magnesium sulfate solution refined from asbestos tailings and a preparation method thereof. The method comprises the following steps: roasting and activating asbestos tailing powder to obtain a roasted and activated product; mixing the roasted and activated product with a leaching reagent to carry out leaching reaction, and adjusting the pH value of a reaction solution in the reaction process to obtain a reaction product; the reaction product was filtered to obtain a refined magnesium sulfate solution. The magnesium sulfate solution refined from the asbestos tailings comprises the magnesium sulfate solution prepared by the method. The beneficial effects of the invention include: the pH value is adjusted to control the leaching of a very small amount of iron ions, the refined magnesium sulfate solution is prepared by a one-step method, and the operation is simple.
Description
Technical Field
The invention relates to the technical field of extraction of valuable components of solid waste, in particular to a magnesium sulfate solution refined from asbestos tailings and a preparation method thereof.
Background
China has rich asbestos mineral resources and is the third place in the world, but the asbestos ore grade in China is low, and a large amount of asbestos tailings are generated in the production process, so that a large amount of asbestos tailings are accumulated. The accumulation of the asbestos tailings not only causes the waste of mineral resources, but also occupies land resources, and has adverse effects on the surrounding environment and the health of residents. The main components of the asbestos tailings are silicon dioxide and magnesium oxide, and in addition, the asbestos tailings also contain impurities such as aluminum oxide, ferric oxide, ferrous oxide, calcium oxide and the like. The silicon and magnesium in the silicon-magnesium separation solution are separated, and the classical method is to leach components which can react with acid, such as magnesium, aluminum, iron, nickel, calcium, potassium, sodium and the like into filtrate by an acid leaching method so as to achieve the purpose of separating the magnesium from the silicon. And because the iron ion reaction activity is high, in order to obtain high-purity magnesium-containing series compound products, the iron ion must be removed from the solution at first, and the method has complex operation flow and difficult operation.
The existing treatment method has the defects of complex preparation process flow of the refined magnesium sulfate solution, difficult operation and the like. A method for refining magnesium sulfate solution with simple operation and high magnesium ion leaching rate is urgently needed to solve the defects of the prior art.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a method for refining a magnesium sulfate solution from asbestos tailings, which has a simple process.
In order to achieve the purpose, the invention provides a method for refining a magnesium sulfate solution from asbestos tailings. The method comprises the following steps: roasting and activating the asbestos tailing powder to obtain a roasted and activated product; mixing the roasted and activated product with a leaching agent to carry out leaching reaction, and adjusting the pH value of a reaction solution in the reaction process to obtain a reaction product; the reaction product was filtered to obtain a refined magnesium sulfate solution.
According to an exemplary embodiment of the invention, the asbestos tailings may comprise the following components in mass percent: siO 2 2 37.0 to 42.0 percent of MgO, 36.0 to 42.0 percent of Al 2 O 3 0.8% -1.2%, TFe 2 O 3 3.0 to 8.0 percent of CaO, 0.4 to 0.7 percent of CaO and 12.0 to 13.5 percent of loss on ignition.
According to an exemplary embodiment of the present invention, the asbestos tailings may include, in parts by mass: 37.0 to 42.0 portions of SiO 2 36.0 to 42.0 portions of MgO and 0.8 to 1.2 portions of Al 2 O 3 3.0 to 8.0 portions of TFe 2 O 3 0.4 to 0.7 portion of CaO.
According to an exemplary embodiment of the invention, the mineral phases of the asbestos tailings may include serpentine, talc, magnetite, brucite and chlorite.
According to an exemplary embodiment of the present invention, the firing temperature of the firing activation may be 600 to 800 ℃; the roasting time can be 30-90 min.
According to an exemplary embodiment of the present invention, the mineral phases of the roasted activation product may include forsterite, talc, hematite and serpentine.
According to an exemplary embodiment of the invention, the leaching agent may include one or both of ammonium sulfate and ammonium bisulfate; the mole ratio of the leaching reagent to the asbestos tailings can be 2-4.
According to an exemplary embodiment of the invention, the liquid-to-solid ratio of the leaching reaction may be 14-20 ml/g; the reaction temperature of the leaching reaction can be 15-60 ℃, and the reaction time can be 30-60 min.
According to an exemplary embodiment of the present invention, the pH of the solution is adjusted to 4 to 5 using an acid solution; wherein, the acid solution can comprise sulfuric acid solution, and the concentration of the sulfuric acid solution can be 0.5-5 mol/L.
In another aspect, the present invention provides a magnesium sulfate solution refined from asbestos tailings.
The magnesium sulfate solution may include a magnesium sulfate solution prepared by the method for refining a magnesium sulfate solution from asbestos tailings as described above.
According to an exemplary embodiment of the invention, mg in the magnesium sulfate solution 2+ The leaching rate of the Fe-based alloy is 55 to 65 percent, and the leaching rate of the Fe ions is 0.34 to 5.33 percent.
Compared with the prior art, the invention has the beneficial effects of at least one of the following contents:
(1) The reaction activity of the product of the asbestos tailings after roasting and activation is increased, and the leaching efficiency of magnesium ions is increased.
(2) One or more of ammonium bisulfate and ammonium sulfate solution are adopted for leaching, and the technical foundation can be laid for the recycling of waste liquid by adopting sulfuric acid to adjust the pH value.
(3) Sulfuric acid is added to adjust the pH value of the reaction during leaching, a small amount of iron ions are controlled to be leached, the refined magnesium sulfate solution is prepared in one step, the operation is simple, the process is simple, the energy consumption is low, and the accumulated asbestos tailings can be consumed.
(4) Mg in magnesium sulfate solution refined by the invention 2+ The leaching rate of the Fe-based alloy is more than 55 percent and can reach 65 percent at most, and the leaching rate of the Fe ions is less than 6 percent and can reach 0.34 percent at least.
(5) The invention uses the asbestos tailing roasting product mainly containing serpentine to leach and extract magnesium oxide component and separate the magnesium oxide component from silicon dioxide residue, and obtains refined magnesium sulfate solution through one-step leaching, which can be used for preparing series magnesium-containing compound products, and the silicon dioxide residue can be used for preparing series silicon-containing compound products, thereby realizing the resource utilization of solid waste, and having important significance for resource and environmental protection and ecological and sustainable development.
Drawings
The above and other objects and features of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
fig. 1 shows XRD patterns before and after firing of asbestos tailings in accordance with an exemplary embodiment of the present invention;
figure 2 shows an XRD pattern of a leach residue according to an exemplary embodiment of the present invention.
Detailed Description
The present invention will be better understood by those skilled in the art from the following detailed description taken in conjunction with the accompanying drawings.
The biggest problem in preparing the refined magnesium sulfate solution by selectively leaching the asbestos tailing roasted product is the leaching inhibition of iron ions, and the leaching pH of the iron ions and the magnesium ions are different according to thermodynamic data. Therefore, the leaching rate of iron and magnesium can be further controlled by controlling the pH value, so that the process flow of preparing the refined magnesium sulfate can be simplified, and the industrial cost can be saved.
Exemplary embodiment 1
The present exemplary embodiment provides a method for refining a magnesium sulfate solution from asbestos tailings. The method may comprise the steps of:
s1, roasting and activating the asbestos tailing powder to obtain a roasted and activated product.
In this embodiment, the asbestos tailings comprise the following components in percentage by mass:
SiO 2 37.0% -42.0%, such as 38.0%, 39.0%, 40.0%, 41.0%, 41.5%;
MgO is 36.0% -42.0%, for example 37.0%, 38.0%, 39.0%, 40.0%, 41.0%;
Al 2 O 3 0.8% to 1.2%, for example 0.9%, 1.0%, 1.1%;
TFe 2 O 3 3.0% to 8.0%, for example 3.5%, 4.0%, 5.0%, 6.0%, 7.0%, 7.5%;
CaO is 0.4% to 0.7%, for example 0.5% or 0.6%.
In this embodiment, the loss on ignition of the asbestos tailings is 12.0% to 13.5%, for example, 12.5%, 13.0%.
In other words, siO in asbestos tailings 2 、MgO、Al 2 O 3 、TFe 2 O 3 CaO mass ratio of 37.0-42.0: 36.0-42.0: 0.8 to 1.2: 3.0-8.0: 0.4 to 0.7.
In this example, as shown in fig. 1, the mineral species contained in the asbestos tailings powder is mainly serpentine, and a small amount of at least one of talc, magnetite, brucite, and chlorite is also contained.
In this embodiment, the roasting temperature for roasting activation may be 600 to 800 ℃, such as 650 ℃, 700 ℃, and 750 ℃; the roasting time can be 30 min-90 min, such as 35min, 40min, 55min, 60min, 70min, 75min, 80min, 85min. The main purpose of roasting is to destroy serpentine structure and promote subsequent magnesium ion leaching. When the roasting temperature is too low or the roasting time is too short, the damage degree of the serpentine structure is low, and the leaching rate of magnesium ions is reduced; when the calcination temperature is too high or the calcination time is too long, the formed forsterite increases and the leaching rate of magnesium ions also decreases.
The decomposition principle of the serpentine Dan Beishao is that after the asbestos tailings are roasted, the main phase serpentine in the tailings is subjected to dehydroxylation reaction to remove structural water, and the structure of the serpentine is decomposed and destroyed to form an amorphous compound, so that the extraction rate of MgO is improved.
Serpentine Dan Beishao decomposition formula: mg (Mg) 3 Si 2 O 5 (OH) 4 ＝3MgO+2SiO 2 +2H 2 O↑
In this example, as shown in FIG. 1, the mineral phases of the calcined activation product were mainly forsterite, talc, hematite and undecomposed serpentine.
S2, mixing the roasted and activated product with a leaching reagent to carry out leaching reaction, and adjusting the pH value of a reaction solution in the reaction process to obtain a reaction product.
In this example, the leaching principle is:
nMgO·mFe 2 O 3 ·xSiO 2 +(m+n)(NH 4 ) 2 SO 4 ＝xSiO 2 ↓+nMgSO 4 +mFe 2 O 3 ↓+(m+n)NH 3 ↑
nMgO·mFe 2 O 3 ·xSiO 2 +NH 4 HSO 4 ＝xSiO 2 ↓+nMgSO 4 +mFe 2 O 3 ↓+(m+n)NH 3 ↑
the invention treats asbestos tailings, firstly adopts a roasting method to destroy a serpentine structure through high temperature, then adds ammonium sulfate or ammonium bisulfate for leaching, and adds sulfuric acid to adjust the pH value of a leaching reaction in the leaching process so as to leach magnesium ions as much as possible under the condition of extremely small amount of iron ions.
In this example, the leaching agent includes one or both of ammonium sulfate and ammonium bisulfate. In consideration of the influence on the environment, the selected ammonium sulfate and ammonium bisulfate are chemical additives which have less pollution on the environment and can be recycled.
In this example, the molar ratio of leaching agent to the asbestos tailings is 2 to 4, for example 2.5, 3, 3.5. Too low a molar ratio results in low leaching rate of magnesium ions, and too high a molar ratio results in waste of reagents.
In this example, the liquid-solid ratio of the leaching reaction may be 14 to 20ml/g, for example 15ml/g, 16ml/g, 17ml/g, 18ml/g, 19ml/g, and too high a liquid-solid ratio may result in too slow a reaction rate. Wherein, the liquid-solid ratio refers to the ratio of the volume of the leaching agent to the mass of the roasted activated product.
In this example, the leaching reaction temperature is 15 ℃ to 60 ℃, for example, 16 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 50 ℃, 55 ℃; too low a leaching reaction temperature will inhibit the reaction rate, while too high a reaction temperature will be energy intensive and uneconomical. The leaching reaction time is 30 min-60 min, such as 35min, 40min, 45min, 50min and 55min. Too short a time may result in incomplete reaction, and too long a time may result in increased energy consumption.
In this example, the solution pH is adjusted to 4 to 5, e.g. 4.1, 4.3, 4.5, 4.7, 4.9, using an acid solution. Too low a pH leads to an increase in the leaching rate of iron ions, and too high a pH leads to a decrease in the leaching rate of magnesium ions. Wherein the acid solution comprises a sulfuric acid solution, and the concentration of the sulfuric acid solution is 0.5-5 mol/L, such as 1mol/L, 2mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L. Ammonium bisulfate and ammonium sulfate solutions are relatively weak in acidity, so acid solutions are required to adjust the acidity. In order not to introduce other impurity ions into the reaction solution, the adjustment of pH is performed using a sulfuric acid solution.
And S3, filtering the reaction product to obtain a refined magnesium sulfate solution.
Exemplary embodiment 2
The present exemplary embodiment provides a magnesium sulfate solution refined from asbestos tailings, including a magnesium sulfate solution prepared by the method for refining a magnesium sulfate solution from asbestos tailings.
In this example, mg in magnesium sulfate solution 2+ The leaching rate of the Fe-based alloy is 55 to 65 percent, and the leaching rate of the Fe ions is 0.34 to 5.33 percent. Refining Mg in magnesium sulfate solution 2+ The leaching rate of the Fe-based alloy is more than 55 percent and can reach 65 percent at most, and the leaching rate of the Fe ions is less than 5.33 percent and can reach 0.34 percent at least. Here, the leaching rate of Fe ion means Fe 3+ And Fe 2+ Sum of leaching rates. Wherein the leaching rate refers to the metal quilt to be extractedDegree of leaching, e.g. Mg in magnesium sulfate solution 2+ Accounts for Mg in asbestos tailings 2+ 56.35% of (1), then Mg 2+ The leaching rate of (A) is 56.35%.
In this example, fig. 2 shows XRD patterns of the leached residues obtained under different reaction conditions, and it can be seen from fig. 2 that the main phases in the leached residues of the present invention are undecomposed serpentine, forsterite, hematite, etc. Wherein, the molar ratio in figure 2 refers to the molar ratio of the leaching reagent and the asbestos tailings, the pH refers to the pH adjusting value of the reaction solution, the temperature (DEG C) refers to the control temperature of the reaction process, and the time (min) refers to the reaction time.
For a better understanding of the exemplary embodiments of the invention, reference will now be made to the following examples which are set forth to illustrate, but are not to be construed to limit the invention.
Example 1
The chemical components of the akkerite tailings selected in the test are shown in the table 1:
TABLE 1 main chemical composition of asbestos tailings
| Element(s) | SiO 2 | Al 2 O 3 | TFe 2 O 3 | MgO | CaO | Loss on ignition | Others |
| Content w B /％ | 40.33 | 1.20 | 3.09 | 41.59 | 0.47 | 12.74 | 0.58 |
Placing the asbestos tailing powder in a high-temperature furnace, and roasting for 90min at the temperature of 600 ℃ to obtain a roasted activated product, wherein the mineral types contained in the roasted activated product mainly comprise forsterite and hematite and also contain undecomposed serpentine.
Then placing the calcined and activated asbestos tailings into a reaction kettle with stirring and heating functions, adding ammonium sulfate, wherein the molar ratio of the ammonium sulfate to the asbestos tailings is 2.5, controlling the pH value of a solution in the reaction kettle to be 4.0 by using 1mol/L sulfuric acid solution, reacting for 60min under the conditions that the temperature is 15 ℃ and the liquid-solid ratio is 14ml/g, and performing pressure filtration on a product after reaction to obtain a refined magnesium sulfate solution, wherein the leaching rate of iron ions in a filtrate is 0.34%, and the leaching rate of magnesium ions is 56.35%.
Example 2
The chemical components of the chosen Qinghai vast rock rockwool tailings in the test are shown in the following table 2:
table 2 shows the main chemical components of asbestos tailings
| Element(s) | SiO 2 | Al 2 O 3 | TFe 2 O 3 | MgO | CaO | Loss on ignition | Others are |
| Content w B /％ | 37.89 | 0.81 | 6.91 | 40.25 | 0.54 | 13.03 | 0.57 |
Placing asbestos tailing powder in a high-temperature furnace, roasting for 30min at 800 ℃ to obtain a roasted activated product, then placing the roasted activated product in a reaction kettle with stirring and heating functions, adding ammonium bisulfate, wherein the molar ratio of the ammonium bisulfate to the asbestos tailing is 2.0, controlling the pH value of a solution in the reaction kettle to be 4.0 by using 0.5mol/L sulfuric acid solution, reacting for 30min at the temperature of 60 ℃ and the liquid-solid ratio of 20ml/g, and performing pressure filtration on a product after the reaction to obtain a refined magnesium sulfate solution, wherein the leaching rate of iron ions in a filtrate is 3.40%, and the leaching rate of magnesium ions is 60.40%.
Example 3
The chemical components of the akkerite tailings selected in the test are shown in table 3:
table 3 shows the main chemical components of asbestos tailings
| Element(s) | SiO 2 | Al 2 O 3 | TFe 2 O 3 | MgO | CaO | Loss on ignition | Others |
| Content w B /％ | 40.33 | 1.20 | 3.09 | 41.59 | 0.47 | 12.74 | 0.58 |
Placing asbestos tailing powder in a high-temperature furnace, roasting for 90min at the temperature of 650 ℃ to obtain a roasted activated product, then placing the roasted activated product in a reaction kettle with stirring and heating functions, adding ammonium sulfate, wherein the molar ratio of the ammonium sulfate to the asbestos tailing is 4.0, controlling the pH value of a solution in the reaction kettle to be 5.0 by using 0.5mol/L sulfuric acid solution, reacting for 30min at the temperature of 40 ℃ and the liquid-solid ratio of 20ml/g, and performing pressure filtration on a product after the reaction to obtain a refined magnesium sulfate solution, wherein the leaching rate of iron ions in a filtrate is 0.43 percent, and the leaching rate of magnesium ions is 55.69 percent.
Example 4
The chemistry of the selected shanxi da An asbestos tailings is shown in table 4:
table 4 shows the main chemical components of asbestos tailings
| Element(s) | SiO 2 | Al 2 O 3 | TFe 2 O 3 | MgO | CaO | Loss on ignition | Others are |
| Content w B /％ | 37.69 | 1.20 | 7.75 | 40.13 | 0.42 | 12.5 | 0.31 |
Placing the asbestos tailing powder in a high-temperature furnace, roasting for 90min at the temperature of 650 ℃ to obtain a roasted activated product, then placing the roasted activated product in a reaction kettle with stirring and heating functions, adding ammonium bisulfate, wherein the molar ratio of the ammonium bisulfate to the asbestos tailing is 2.0, controlling the pH value of a solution in the reaction kettle to be 5.0 by using 1mol/L sulfuric acid solution, reacting for 45min at the temperature of 50 ℃ and the liquid-solid ratio of 14ml/g, and performing pressure filtration on a product after the reaction to obtain a refined magnesium sulfate solution, wherein the leaching rate of iron ions in a filtrate is 5.33%, and the leaching rate of magnesium ions is 65.0%.
Example 5
The chemistry of the selected shanxi da An asbestos tailings is shown in table 5:
TABLE 5 main chemical composition of asbestos tailings
| Element(s) | SiO 2 | Al 2 O 3 | TFe 2 O 3 | MgO | CaO | Loss on ignition | Others |
| Content w B /％ | 37.69 | 1.20 | 7.75 | 40.13 | 0.42 | 12.5 | 0.31 |
Placing the asbestos tailing powder in a high-temperature furnace, roasting for 40min at 800 ℃ to obtain a roasted activated product, then placing the roasted activated product in a reaction kettle with stirring and heating functions, adding ammonium bisulfate, wherein the molar ratio of the ammonium bisulfate to the asbestos tailing is 4.0, controlling the pH value of a solution in the reaction kettle to be 4.0 by using 5mol/L sulfuric acid solution, reacting for 30min at the temperature of 40 ℃ and the liquid-solid ratio of 20ml/g, and performing pressure filtration on a product after the reaction to obtain a refined magnesium sulfate solution, wherein the leaching rate of iron ions in a filtrate is 2.24%, and the leaching rate of magnesium ions is 61.34%.
In conclusion, the method can adjust the pH value of the reaction by sulfuric acid, control the leaching of a very small amount of iron ions, prepare the refined magnesium sulfate solution by a one-step method, and is simple to operate; mg in magnesium sulfate solution refined by the invention 2+ The leaching rate of the Fe-based alloy is more than 55 percent and can reach 65 percent to the maximum, and the leaching rate of the Fe ions is less than 5.33 percent and can reach 0.34 percent to the minimum; and the asbestos tailings can be recycled, so that the land resource is saved, and the environment is protected.
Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for refining magnesium sulfate solution from asbestos tailings is characterized by comprising the following steps:
roasting and activating asbestos tailing powder to obtain a roasted and activated product;
mixing the roasted and activated product with a leaching reagent to carry out leaching reaction, and adjusting the pH value of a reaction solution in the reaction process to obtain a reaction product;
the reaction product was filtered to obtain a refined magnesium sulfate solution.
2. The method for refining the magnesium sulfate solution by using the asbestos tailings as claimed in claim 1, wherein the asbestos tailings comprise the following components in percentage by mass: siO 2 2 37.0-42.0 percent of MgO, 36.0-42.0 percent of Al 2 O 3 0.8% -1.2%, TFe 2 O 3 3.0 to 8.0 percent of CaO, 0.4 to 0.7 percent of CaO and 12.0 to 13.5 percent of loss on ignition.
3. The method for refining the magnesium sulfate solution by using the asbestos tailings as claimed in claim 1, wherein the mineral phases of the asbestos tailings comprise serpentine, talc, magnetite, brucite and chlorite.
4. The method for refining the magnesium sulfate solution from the asbestos tailings according to claim 1, wherein the roasting temperature for roasting and activating is 600-800 ℃; the roasting time is 30-90 min.
5. The method for refining the magnesium sulfate solution from the asbestos tailings as claimed in claim 1, wherein the mineral phases of the roasted activated product comprise forsterite, talc, hematite and undecomposed serpentine.
6. The method for refining the magnesium sulfate solution from the asbestos tailings according to claim 1, wherein the leaching agent comprises one or both of ammonium sulfate and ammonium bisulfate; the mole ratio of the leaching reagent to the asbestos tailings is 2-4.
7. The method for refining the magnesium sulfate solution from the asbestos tailings according to the claim 1, wherein the liquid-solid ratio of the leaching reaction is 14-20 ml/g;
the reaction temperature of the leaching reaction is 15-60 ℃, and the reaction time is 30-60 min.
8. The method for refining the magnesium sulfate solution from the asbestos tailings according to claim 1, wherein an acid solution is used for adjusting the pH of the solution to 4-5; wherein the content of the first and second substances,
the acid solution comprises sulfuric acid solution, and the concentration of the sulfuric acid solution is 0.5-5 mol/L.
9. A magnesium sulfate solution refined from asbestos tailings, wherein the magnesium sulfate solution comprises the magnesium sulfate solution prepared by the method for refining the magnesium sulfate solution from asbestos tailings according to any one of claims 1 to 8.
10. The magnesium sulfate solution refined from asbestos tailings as claimed in claim 9, wherein Mg in the magnesium sulfate solution 2+ The leaching rate of the Fe-based alloy is 55 to 65 percent, and the leaching rate of the Fe ions is 0.34 to 5.33 percent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115991496A (en) * | 2023-02-22 | 2023-04-21 | 西南科技大学 | Preparation method of hydrated magnesium ammonium sulfate |
| CN116081659A (en) * | 2023-01-19 | 2023-05-09 | 西南科技大学 | Asbestos tailing refined magnesium sulfate solution and method and application thereof |
| CN116081660A (en) * | 2023-02-22 | 2023-05-09 | 西南科技大学 | Preparation method of hydrated ammonium sulfate salt |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT177406B (en) * | 1952-07-02 | 1954-01-25 | Steirische Magnesit Ind Ag | Process for the production of pure magnesium salts |
| CN104030328A (en) * | 2014-06-27 | 2014-09-10 | 西南科技大学 | Method for extracting magnesium oxide and preparing active porous silicon dioxide material by using serpentine |
| CN104891537A (en) * | 2015-05-20 | 2015-09-09 | 南阳东方应用化工研究所 | Comprehensive utilization method of silicate minerals |
| CN104905983A (en) * | 2015-05-19 | 2015-09-16 | 河北工程大学 | Method for extracting mineral bath salt from asbestos tailings |
| CN107915242A (en) * | 2017-05-30 | 2018-04-17 | 张旭 | Asbestos tailings prepare method of magnesium oxide |
| CN108358290A (en) * | 2018-03-15 | 2018-08-03 | 湖南隆洲驰宇科技有限公司 | A kind of preparation method of iron-based arsenic passivating material, the iron-based arsenic passivating material and application thereof being prepared by this method |
| CN110759365A (en) * | 2018-07-25 | 2020-02-07 | 张旭 | Device for preparing magnesium hydroxide by leaching solid magnesium ore and use method |
| CN114873615A (en) * | 2022-05-24 | 2022-08-09 | 西南科技大学 | Method for preparing magnesium sulfate by removing iron from asbestos tailings |
-
2022
- 2022-08-24 CN CN202211021837.5A patent/CN115259186B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT177406B (en) * | 1952-07-02 | 1954-01-25 | Steirische Magnesit Ind Ag | Process for the production of pure magnesium salts |
| CN104030328A (en) * | 2014-06-27 | 2014-09-10 | 西南科技大学 | Method for extracting magnesium oxide and preparing active porous silicon dioxide material by using serpentine |
| CN104905983A (en) * | 2015-05-19 | 2015-09-16 | 河北工程大学 | Method for extracting mineral bath salt from asbestos tailings |
| CN104891537A (en) * | 2015-05-20 | 2015-09-09 | 南阳东方应用化工研究所 | Comprehensive utilization method of silicate minerals |
| CN107915242A (en) * | 2017-05-30 | 2018-04-17 | 张旭 | Asbestos tailings prepare method of magnesium oxide |
| CN108358290A (en) * | 2018-03-15 | 2018-08-03 | 湖南隆洲驰宇科技有限公司 | A kind of preparation method of iron-based arsenic passivating material, the iron-based arsenic passivating material and application thereof being prepared by this method |
| CN110759365A (en) * | 2018-07-25 | 2020-02-07 | 张旭 | Device for preparing magnesium hydroxide by leaching solid magnesium ore and use method |
| CN114873615A (en) * | 2022-05-24 | 2022-08-09 | 西南科技大学 | Method for preparing magnesium sulfate by removing iron from asbestos tailings |
Non-Patent Citations (1)
| Title |
|---|
| 朱存金等: ""以温石棉尾矿为镁源制备碱式硫酸镁晶须"", vol. 35, no. 1, pages 567 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116081659A (en) * | 2023-01-19 | 2023-05-09 | 西南科技大学 | Asbestos tailing refined magnesium sulfate solution and method and application thereof |
| CN115991496A (en) * | 2023-02-22 | 2023-04-21 | 西南科技大学 | Preparation method of hydrated magnesium ammonium sulfate |
| CN116081660A (en) * | 2023-02-22 | 2023-05-09 | 西南科技大学 | Preparation method of hydrated ammonium sulfate salt |
| CN115991496B (en) * | 2023-02-22 | 2024-04-30 | 西南科技大学 | Preparation method of hydrated magnesium ammonium sulfate |
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