CN111530895A - Method for high-stability solidification of arsenic slag and tailing slag - Google Patents
Method for high-stability solidification of arsenic slag and tailing slag Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 176
- 238000000034 method Methods 0.000 title claims abstract description 91
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 63
- 238000007711 solidification Methods 0.000 title claims description 33
- 230000008023 solidification Effects 0.000 title claims description 33
- GSYZQGSEKUWOHL-UHFFFAOYSA-N arsenic calcium Chemical compound [Ca].[As] GSYZQGSEKUWOHL-UHFFFAOYSA-N 0.000 claims abstract description 54
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000003723 Smelting Methods 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 30
- 230000009471 action Effects 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 238000007885 magnetic separation Methods 0.000 claims abstract description 22
- 239000002699 waste material Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 16
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 238000005194 fractionation Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000033228 biological regulation Effects 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 5
- 229940000489 arsenate Drugs 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 claims description 4
- 229940103357 calcium arsenate Drugs 0.000 claims description 4
- RTFOOERBKBOMSV-UHFFFAOYSA-L calcium;hydrogen arsorate Chemical compound [Ca+2].O[As]([O-])([O-])=O RTFOOERBKBOMSV-UHFFFAOYSA-L 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005188 flotation Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052840 fayalite Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 9
- 230000006641 stabilisation Effects 0.000 abstract description 9
- 238000011105 stabilization Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009270 solid waste treatment Methods 0.000 abstract description 2
- 238000001029 thermal curing Methods 0.000 abstract 1
- 239000002910 solid waste Substances 0.000 description 18
- ZGOFOSYUUXVFEO-UHFFFAOYSA-N [Fe+4].[O-][Si]([O-])([O-])[O-] Chemical compound [Fe+4].[O-][Si]([O-])([O-])[O-] ZGOFOSYUUXVFEO-UHFFFAOYSA-N 0.000 description 15
- 230000007613 environmental effect Effects 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 238000002386 leaching Methods 0.000 description 12
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- 238000005406 washing Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000003993 interaction Effects 0.000 description 6
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
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- 239000002019 doping agent Substances 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 231100000419 toxicity Toxicity 0.000 description 5
- 230000001988 toxicity Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000004568 cement Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000005538 encapsulation Methods 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- 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
- C01B33/20—Silicates
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a solid waste treatment method, in particular to a method for solidifying arsenic slag and tailing slag with high stability, which comprises the steps of firstly carrying out magnetic fractionation on the tailing slag in a weakly acidic, neutral or weakly alkaline environment aqueous solution, recycling magnetite components in the tailing slag after separation, and synchronously obtaining tailing residues; carrying out thermocuring stabilization on the tailing raw slag obtained in the step, the separated magnetite or the residual ferric orthosilicate and the arsenic-calcium slag generated by smelting under the composite action of certain conditions; the invention provides a unique method, realizes resource utilization of valuable substances in the tailing slag by magnetic separation in a water solution in a specific environment, realizes waste treatment by waste while realizing resource utilization, and solves the problems of difficult waste treatment and poor treatment effect in the smelting process.
Description
Technical Field
The invention relates to a solid waste treatment method, in particular to a method for solidifying arsenic slag and tailing slag with high stability.
Background
Arsenic and its arsenides are highly toxic substances that form natural minerals in the natural environment often associated with numerous colored elements. In the industrial development and smelting process of the series of non-ferrous metal minerals, the migration and transformation of arsenic-containing substances are easily caused, so that a large amount of arsenic-containing waste residues and the like are finally formed, and the safe, effective and stable solidification treatment of arsenic-containing solid wastes is vital to the improvement of the ecological environment and the human health.
The common arsenic slag solid waste is formed in the chemical precipitation treatment of a calcium method or an iron method of arsenic-containing waste water, the series of methods are widely used due to high treatment efficiency, simplicity and rapidness, and the formed arsenic-containing solid waste has the characteristics of poor stability, high water content and the like and can not reach the treatment standard of environmental protection requirements. Therefore, how to deeply realize the high-stability solidification of the arsenic-calcium waste slag is urgent. At present, aiming at the treatment technologies that the stabilizing and curing method of arsenic-containing solid waste is encapsulation curing and cement-based curing, namely harmful solid waste containing arsenic is encapsulated in an inert base material or mixed with cement and the like, the method has good effect on stabilizing arsenic-containing solid waste, but is limited by the price of a matrix material, the coating difficulty and the easiness in forming larger amount of solid waste, so that the method is difficult to be applied on a large scale.
The tailing slag is regarded as low-value industrial waste as tail end waste slag generated in the smelting process, is often treated in a piling and burying mode, occupies a large storage area every year, and consumes a large amount of cost. At present, a method for realizing the resource utilization of valuable substances in tailing slag by magnetic separation in a water solution in a specific environment and simultaneously carrying out efficient stable solidification on arsenic-containing solid waste by using tailing raw slag, separated products and residues does not exist.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for high-stability solidification of arsenic-containing solid waste, which is unique, realizes resource utilization of valuable substances in tailing slag by magnetic separation in a specific environment aqueous solution, and simultaneously utilizes the original tailings, separated products and residues of the tailings to perform high-efficiency stable solidification of the arsenic-containing solid waste.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for high-stability solidification of arsenic slag and tailings slag is characterized by comprising the following steps: the method comprises the following steps:
a. separation of tailing slag: carrying out magnetic fractionation on the tailing slag in a weakly acidic, neutral or weakly alkaline environment aqueous solution, and recycling magnetite components in the tailing slag after separation to synchronously obtain tailing residue ferric orthosilicate;
b. b, carrying out solidification and stabilization on the tailing raw slag obtained in the step a, the separated magnetite or the residual ferric orthosilicate and the arsenic-calcium slag generated by smelting under the composite action of certain conditions;
the magnetic fractionation process refers to the magnetic adsorption separation of the tailing slag in different environments, the magnetic separation temperature is 25-55 ℃, the separation time is 1-7h, and the solid-liquid ratio of the tailing slag to the environment is 1:2-1: 30;
the weak acidity, near neutrality or weak alkalinity refers to a water solution with pH of 4.5-6.5, 6.5-7.5 and 7.5-9.5;
the composite action process comprises the action of tailings raw slag and arsenic-calcium slag, the action of separating magnetite from arsenic-calcium slag or the action of residual slag and arsenic-calcium slag, wherein the mass ratio of the composite action process is 0.1:1-3:1, the temperature is 200-700 ℃, the composite action time is 1-8 h, and the composite action atmosphere is air or nitrogen;
the tailing slag is tail slag generated in a high-temperature smelting process, is derived from smelting slag generated in a low-blowing smelting or PS converter blowing process, and is formed by slag cooling and flotation, and the arsenic-containing waste slag is arsenic-calcium slag, arsenic slag generated in the calcium method treatment of arsenic-containing wastewater, calcium hydrogen arsenate monohydrate, calcium hydroxy arsenate, calcium arsenate or a mixture thereof;
the magnetic separation in the step a is carried out to obtain magnetite and magnetite-like substances slightly doped with other elements, and the residual tailing slag is ferric orthosilicate and ferric orthosilicate slightly doped with other elements;
the weak acidity regulation adopts dilute hydrochloric acid, and the weak alkalinity regulation adopts dilute sodium hydroxide;
the magnetite or magnetite-like compound is Fe3O4Or Fe2.95Si0.05O4(ii) a The residual tailing slag is Fe2SiO4Or MFeSi2O6；
And M is Mg, Ca, Al, Cu and the like.
Compared with the prior art, the invention has the following beneficial effects:
1) the method is unique: the method provided by the invention comprises the steps of carrying out magnetic fractionation on the tailing slag in a weakly acidic, neutral or weakly alkaline environment aqueous solution, recycling magnetite components in the tailing slag after separation, and synchronously obtaining tailing residues; the tailing raw slag obtained in the step, the separated magnetite or the residual ferric orthosilicate and the arsenic-calcium slag generated by smelting are subjected to composite action under certain conditions for solidification and stabilization; the method can realize the resource utilization of valuable products in the tailing slag, simultaneously realize the low-cost and high-efficiency solidification of arsenic-containing solid waste in the smelting industry, has the advantages of simple treatment process, wide application range and the like, and solves the problems of complex solidification and stabilization process, poor effect and the like of the arsenic slag.
2) Realizing the treatment of wastes with processes of wastes against one another: the tailing slag in the method is tail slag generated in a high-temperature smelting process, is derived from smelting slag generated in a low-blowing smelting or PS converter blowing process, and is formed by slag cooling and flotation, wherein the arsenic-containing waste slag is arsenic-calcium slag, arsenic slag generated in the calcium treatment of arsenic-containing wastewater, calcium hydrogen arsenate monohydrate, calcium hydroxy arsenate, calcium arsenate or a mixture of the arsenic slag and the calcium hydroxy arsenate; the method can realize resource utilization of the waste tailing slag, and can stabilize and solidify the arsenic-calcium slag by utilizing the characteristics of the product while recovering the product, thereby realizing treatment of wastes with processes of wastes against one another.
3) The method provided by the invention can realize effective strong operability of stabilizing and curing the arsenic-calcium slag by utilizing the waste tailing slag, and realizes low-cost, convenient and efficient disposal of the arsenic-containing waste slag.
4) The method provided by the invention has obvious effects on realizing comprehensive resource utilization, reduction and stable solidification of the waste slag of smelting wastes.
Drawings
FIG. 1 is a schematic view showing the process of the present invention for high-stability solidification and resource utilization of arsenic slag and tailings slag.
FIG. 2 is an XRD pattern of the separation and resource utilization process of tailing slag.
FIG. 3 shows the arsenic leaching concentration of the slag and the separated substances after the arsenic-calcium slag is stably solidified.
Detailed Description
The following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1: a method for high-stability solidification of arsenic slag and tailing slag is characterized in that tailing slag environmental aqueous solution generated in a smelting process is coupled with a magnetic separation resource for recycling. The specific implementation method comprises the following steps: weighing a certain amount of smelting tailing slag, adding a weakly acidic aqueous solution with the pH value of 5.5, performing a water phase separation experiment on valuable components of the tailing slag at the ratio of 1:10 to an environmental aqueous solution, at the temperature of 25 ℃, at 500rmp and under the condition that the interaction time is 3h, subsequently performing magnet separation, washing and drying to obtain a magnetite product, and performing suction filtration separation, washing and drying on residual solids and residual solution to obtain the ferric metasilicate product. The product mass was weighed separately and the yield was calculated to be 68.1 wt% solids of the separated magnetite, 30.3 wt% iron orthosilicate and 1.6% others (not separated). The phase X-ray diffraction measurement is shown in FIG. 2.
Example 2: a method for high-stability solidification of arsenic slag and tailing slag is characterized in that tailing slag environmental aqueous solution generated in a smelting process is coupled with a magnetic separation resource for recycling. The specific implementation method comprises the following steps: weighing a certain amount of smelting tailing slag, adding a neutral aqueous solution with the pH value of 7.0, performing a water phase separation experiment on valuable substance components of the tailing slag under the conditions that the ratio of the tailing slag to the environmental aqueous solution is 1:10, the temperature is 25 ℃, the rmp is 500 and the interaction time is 3 hours, subsequently performing magnetic separation, washing and drying to obtain a magnetite product, and performing suction filtration separation, washing and drying on residual solids and residual solution to obtain an iron orthosilicate product. The product mass was weighed separately and the yield was calculated to be 66.7 wt% solids of separated magnetite, 27.6 wt% iron orthosilicate and 5.7 wt% others (not separated). The phase X-ray diffraction measurement is shown in FIG. 2.
Example 3: a method for high-stability solidification of arsenic slag and tailing slag is characterized in that tailing slag environmental aqueous solution generated in a smelting process is coupled with a magnetic separation resource for recycling. The specific implementation method comprises the following steps: weighing a certain amount of smelting tailing slag, adding a weakly alkaline aqueous solution with the pH value of 8.5, performing a water phase separation experiment on valuable substance components of the tailing slag under the conditions that the ratio of the tailing slag to the environmental aqueous solution is 1:10, the temperature is 25 ℃, the rmp is 500 and the interaction time is 3 hours, subsequently performing magnetic separation, washing and drying to obtain a magnetite product, and performing suction filtration separation, washing and drying on residual solids and residual solution to obtain the ferric metasilicate product. The product mass was weighed separately and the yield was calculated to be 72.7 wt% solids of the isolated magnetite, 25.9 wt% solids of the iron orthosilicate and 1.4 wt% solids of the rest (not isolated). The phase X-ray diffraction pattern is shown in fig. 2.
Example 4: a method for high-stability solidification of arsenic slag and tailing slag is characterized in that tailing slag environmental aqueous solution generated in a smelting process is coupled with a magnetic separation resource for recycling. The specific implementation method comprises the following steps: weighing a certain amount of smelting tailing slag, adding a weakly acidic aqueous solution with the pH value of 5.5, performing a water phase separation experiment on valuable components of the tailing slag at the ratio of 1:10 to an environmental aqueous solution, at the temperature of 50 ℃, at 500rmp and under the condition that the interaction time is 3h, subsequently performing magnet separation, washing and drying to obtain a magnetite product, and performing suction filtration separation, washing and drying on residual solids and residual solution to obtain the ferric metasilicate product. The product mass was weighed separately and the yield was calculated to be 64.9 wt% for the separated magnetite solids, 34.3 wt% for the iron orthosilicate and 0.8% for the others (not separated).
Example 5: a method for high-stability solidification of arsenic slag and tailing slag is characterized in that tailing slag environmental aqueous solution generated in a smelting process is coupled with a magnetic separation resource for recycling. The specific implementation method comprises the following steps: weighing a certain amount of smelting tailing slag, adding a weakly acidic aqueous solution with the pH value of 5.5, performing a water phase separation experiment on valuable components of the tailing slag at the ratio of 1:20 to an environmental aqueous solution, at the temperature of 50 ℃, at 500rmp and under the condition that the interaction time is 3h, subsequently performing magnet separation, washing and drying to obtain a magnetite product, and performing suction filtration separation, washing and drying on residual solids and residual solution to obtain the ferric metasilicate product. The product mass was weighed separately and the yield was calculated to be 65.3 wt% for the separated magnetite solids, 34.1 wt% for the iron orthosilicate and 0.6% for the others (not separated).
Example 6: the magnetite and iron orthosilicate obtained by separation according to examples 1-4 and the raw tailings as thermal dopants were subjected to highly stable solidification of arsenic slag. The specific implementation method comprises the following steps: weighing a certain amount of tailing raw slag, carrying out compound stabilization and solidification research on the tailing raw slag and arsenic-calcium slag according to the conditions that the mass ratio of the tailing slag to the arsenic-calcium slag is 1:3, the compound action temperature is 400 ℃, the compound time is 4 hours, and the nitrogen flow is 100mL/min, carrying out solid waste toxicity leaching experiment (TCLP) test on the stabilized arsenic-calcium slag and untreated arsenic-calcium slag, wherein the test shows that the leaching concentration of the formed compound arsenic is 3.94mg/L, and the arsenic-fixing rate of the compound is 25.6 wt% by adopting a dissolved inductance coupling plasma mass spectrometer.
Example 7: the magnetite and iron orthosilicate obtained by separation according to examples 1-4 and the raw tailings as thermal dopants were subjected to highly stable solidification of arsenic slag. The specific implementation method comprises the following steps: weighing a certain amount of an iron orthosilicate product obtained by magnetic separation, performing composite stabilization and solidification research on the iron orthosilicate and the arsenic-calcium slag according to the conditions that the mass ratio of the iron orthosilicate to the arsenic-calcium slag is 1:3, the composite action temperature is 400 ℃, the composite time is 4h, and the nitrogen flow is 100mL/min, performing solid waste toxicity leaching experiment (TCLP) test on the stabilized arsenic-calcium slag and the untreated arsenic-calcium slag, wherein the test shows that the arsenic leaching concentration of the arsenic-calcium slag stably solidified by the iron orthosilicate is 14.65mg/L, and the arsenic-fixing rate of a composite substance is 22.42 wt% by adopting a dissolved inductance coupling plasma mass spectrometer.
Example 8: the magnetite and iron orthosilicate obtained by separation according to examples 1-4 and the raw tailings as thermal dopants were subjected to highly stable solidification of arsenic slag. The specific implementation method comprises the following steps: weighing a certain amount of magnetite product obtained by magnetic separation, carrying out compound stabilization and solidification research on magnetite and arsenic-calcium slag according to the conditions that the mass ratio of the magnetite to the arsenic-calcium slag is 1:3, the compound action temperature is 400 ℃, the compound time is 4h and the nitrogen flow is 100mL/min, carrying out solid waste toxicity leaching experiment (TCLP) test on the stabilized arsenic-calcium slag and the untreated arsenic-calcium slag, wherein the test shows that the arsenic leaching concentration of the magnetite stabilized and solidified arsenic-calcium slag is 2.71mg/L, and the arsenic fixation rate of the compound substance is 26.04 wt% by adopting a dissolved inductance coupling plasma mass spectrometer.
Example 9: the magnetite and iron orthosilicate obtained by separation according to examples 1-4 and the raw tailings as thermal dopants were subjected to highly stable solidification of arsenic slag. The specific implementation method comprises the following steps: weighing a certain amount of magnetite product obtained by magnetic separation, carrying out compound stabilization and solidification research on magnetite and arsenic-calcium slag according to the conditions that the mass ratio of the magnetite to the arsenic-calcium slag is 2:2, the compound action temperature is 400 ℃, the compound time is 4h and the nitrogen flow is 100mL/min, carrying out solid waste toxicity leaching experiment (TCLP) test on the stabilized arsenic-calcium slag and the untreated arsenic-calcium slag, wherein the test shows that the arsenic leaching concentration of the magnetite stabilized and solidified arsenic-calcium slag is 1.05mg/L, and the arsenic fixation rate of the compound substance is 27.88 wt% by adopting a dissolved inductance coupling plasma mass spectrometer.
Example 10: the magnetite and iron orthosilicate obtained by separation according to examples 1-4 and the raw tailings as thermal dopants were subjected to highly stable solidification of arsenic slag. The specific implementation method comprises the following steps: weighing a certain amount of magnetite product obtained by magnetic separation, carrying out compound stabilization and solidification research on magnetite and arsenic-calcium slag according to the conditions that the mass ratio of the magnetite to the arsenic-calcium slag is 2:2, the compound action temperature is 600 ℃, the compound time is 4h and the nitrogen flow is 100mL/min, carrying out solid waste toxicity leaching experiment (TCLP) test on the stabilized arsenic-calcium slag and the untreated arsenic-calcium slag, wherein the test shows that the arsenic leaching concentration of the magnetite stabilized and solidified arsenic-calcium slag is 0.73mg/L, and the arsenic fixation rate of the compound substance is 28.95 wt% by adopting a dissolved inductance coupling plasma mass spectrometer.
The technical purpose and effect of the invention can be better achieved and realized by the following technical scheme.
As a preferable technical scheme of the invention, the tailing slag in the step a is derived from smelting slag generated in the low-blowing smelting or PS converter blowing process, and is formed by slag cooling and flotation.
In a preferred embodiment of the present invention, the weak acidic, neutral or weak alkaline environment solution in step a is 4.5-6.5, 6.5-7.5 or 7.5-9.5, respectively, for example, weak acidic is 5.5, neutral is 7.0 or weak alkaline is 8.5, but the invention is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, dilute hydrochloric acid is adopted for weak acidity regulation; the alkalescence regulation adopts dilute sodium hydroxide;
in a preferred embodiment of the present invention, the magnetic separation in step a is a magnetic adsorption separation.
In a preferred embodiment of the present invention, the magnetic separation temperature in step a is 25 ℃ to 55 ℃, for example, 25 ℃, 35 ℃, 45 ℃ or 55 ℃, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
In a preferred embodiment of the present invention, the magnetic separation time in step a is 1 to 7 hours, for example, 1 hour, 2 hours, 4 hours, 6 hours, or 7 hours, but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the ratio of the tailings residue in step a to the ambient liquid-solid ratio is 1:2 to 1:30, for example, 1:2, 1:6, 1:10, 1:15, 1:20, or 1:30, but the ratio is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
The method provided by the invention is directly carried out on the arsenic-containing solid waste, does not need preliminary pretreatment, is suitable for various types of arsenic-containing solid waste in the smelting industry, and has strong operability.
As a preferable technical scheme of the invention, the magnetic separation in the step a is carried out to obtain magnetite and magnetite-like substances slightly doped with other elements, and the residual tailing slag is ferric orthosilicate and ferric orthosilicate slightly doped with other elements; the magnetite or magnetite-like iron ore being Fe3O4Or Fe2.95Si0.05O4(ii) a The residual tailing slag is Fe2SiO4Or MFeSi2O6(M ═ Mg, Ca, Al, Cu, etc.).
As a preferable technical scheme of the invention, the arsenic-containing waste residue in the step b is arsenic-calcium residue, arsenic residue generated by calcium method treatment of arsenic-containing wastewater, and calcium hydrogen arsenate monohydrate, calcium hydroxy arsenate, calcium arsenate or a mixture thereof.
As the preferable technical scheme of the invention, the compound action process in the step b comprises the action of tailings raw slag and arsenic-calcium slag, the action of separating magnetite and arsenic-calcium slag or the action of residual orthosilicate iron and arsenic-calcium slag after separation, and the arsenic-calcium slag is stably solidified through a plurality of interactions.
In a preferred embodiment of the present invention, the conditional complexing action in step b is a complex mass ratio of 0.1:1 to 3:1, for example 0.1:1, 0.5:1, 1:1, 2:1 or 3:1, but is not limited to the recited values, and other values not recited in this range are also applicable.
In a preferred embodiment of the present invention, the temperature range of the constant-condition combined action in step b is 200 ℃ to 700 ℃, for example, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, or 700 ℃, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
As a preferable technical scheme of the invention, the atmosphere of the certain condition composite action in the step b is air or nitrogen.
As the preferable technical scheme of the invention, the environmental liquid in the step a has important influence on magnetic separation and recovery of products, and the proper pH and temperature of the environmental aqueous solution are favorable for improving the product purity and the separation efficiency.
As a preferable technical scheme of the invention, the mass ratio, the temperature and the atmosphere of the compound action in the step b have important influence on stabilizing the arsenic-calcium slag.
In conclusion, the invention provides a method for high-stability solidification and resource utilization of arsenic slag and tailing slag. On one hand, the tailing slag is separated to realize the resource utilization of magnetite, and meanwhile, the tailing slag or separated products are utilized to perform the stable solidification of arsenic-containing waste slag, and finally, the stable solidification of arsenic slag and the tailing slag resource utilization are realized. Through the two-step process, the arsenic leaching rate of the arsenic-calcium slag treated by the method is low, the arsenic fixation rate is high, and the purpose of treating wastes with processes of wastes against one another is realized.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
In FIG. 2, the following steps: a: raw tailing slag; b, weakly acidic treating magnetically separated magnetite; c, residues left after weakly acidic tailing treatment; d, weakly alkaline treating the magnetically separated magnetite; e, residue left after weakly alkaline treatment of tailings; neutralizing the magnetically separated magnetite; g, neutralizing the residue left after the tailings are treated;
in fig. 3: a: unstably solidifying arsenic-calcium slag; b: arsenic-calcium slag is treated at 400 ℃; c: mixing the arsenic-calcium slag and the ferric metasilicate at 400 ℃; d: mixing the arsenic-calcium slag and the raw tailings at 400 ℃; e: mixing the arsenic-calcium slag and magnetite at 400 ℃ (the mass ratio is 3: 1); f: mixing the arsenic-calcium slag and magnetite at 400 ℃ (mass ratio is 2: 2).
Claims (9)
1. A method for high-stability solidification of arsenic slag and tailings slag is characterized by comprising the following steps: the method comprises the following steps:
a. separation of tailing slag: carrying out magnetic fractionation on the tailing slag in a weakly acidic, neutral or weakly alkaline environment aqueous solution, and recycling magnetite components in the tailing slag after separation to synchronously obtain tailing residue ferric orthosilicate;
b. and (b) solidifying and stabilizing the tailing raw slag obtained in the step (a), the separated magnetite or the residual ferric orthosilicate and arsenic-calcium slag generated by smelting arsenic-containing wastewater calcium method under a certain condition.
2. The method of claim 1, wherein the method comprises the following steps: the magnetic fractionation process refers to the magnetic adsorption separation of the tailing slag in different environments, the magnetic separation temperature is 25-55 ℃, the separation time is 1-7h, and the solid-liquid ratio of the tailing slag to the environment is 1:2-1: 30.
3. The method of claim 1, wherein the method comprises the following steps: the weakly acidic, near neutral or weakly alkaline solution is an aqueous solution with pH of 4.5-6.5, 6.5-7.5 and 7.5-9.5.
4. The method of claim 1, wherein the method comprises the following steps: the composite action process comprises the action of tailings raw slag and arsenic-calcium slag, the action of separating magnetite from arsenic-calcium slag or the action of residual ferric orthosilicate and arsenic-calcium slag, wherein the mass ratio of the composite action process is 0.1:1-3:1, the temperature is 200-700 ℃, the composite action time is 1-8 h, and the composite action atmosphere is air or nitrogen.
5. The method of claim 1, wherein the method comprises the following steps: the tailing slag is tail slag generated in a high-temperature smelting process, is derived from smelting slag generated in a low-blowing smelting or PS converter blowing process, and is formed after slag cooling and flotation, and the arsenic-containing waste slag is arsenic-calcium slag, arsenic slag generated in arsenic-containing wastewater calcium method treatment, calcium hydrogen arsenate monohydrate, calcium hydroxy arsenate, calcium arsenate or a mixture thereof.
6. The method of claim 1, wherein the method comprises the following steps: and a, magnetically classifying and separating to obtain magnetite and magnetite-like substances slightly doped with other elements, wherein the residual tailing slag is ferric orthosilicate and ferric orthosilicate slightly doped with other elements.
7. The method of claim 1, wherein the method comprises the following steps: the weak acidity regulation adopts dilute hydrochloric acid, and the weak alkalinity regulation adopts dilute sodium hydroxide.
8. The method of claim 6, wherein the method comprises the following steps: the magnetite or magnetite-like compound is Fe3O4Or Fe2.95Si0.05O4(ii) a The residual tailing slag is Fe2SiO4Or MFeSi2O6。
9. The method of claim 8, wherein the arsenic slag and the tailings are solidified with high stability, and the method comprises the following steps: and M is Mg, Ca, Al, Cu and the like.
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