CN112458290A - Harmless treatment method for solid waste of nickel-containing iron slag - Google Patents
Harmless treatment method for solid waste of nickel-containing iron slag Download PDFInfo
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- CN112458290A CN112458290A CN202011233610.8A CN202011233610A CN112458290A CN 112458290 A CN112458290 A CN 112458290A CN 202011233610 A CN202011233610 A CN 202011233610A CN 112458290 A CN112458290 A CN 112458290A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
- B09B3/25—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
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- 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 discloses a harmless treatment method of nickel-containing iron slag solid waste, which comprises the following steps: carrying out countercurrent leaching on the nickel-iron-containing slag solid waste by using a weakly acidic aqueous solution, adding an alkaline solution into the obtained acid leaching slag, stirring to adjust the pH value, and then adding an oxidant to obtain oxidized alkaline washing slag; adding water and a calcification agent into the oxidized alkaline washing slag, stirring and calcification, and adding a coagulant and cement to obtain a cementing material; pressing the cementing material into blocks, and then placing the blocks in the shade and dry place for curing for 10 to 15 days to obtain primary curing slag; crushing the primary solidified slag into particles with the particle size of less than 3mm, adding water, cement and sand, stirring, repeating the process for preparing the cementing material, and performing secondary solidification to obtain secondary solidified slag; and (4) carrying out toxicity detection and strength detection on the secondary solidified slag, crushing the secondary solidified slag until the granularity is less than 10mm, and then filling the mine. The invention has simple process and low treatment cost, can utilize the iron slag as resources and is nontoxic and harmless.
Description
Technical Field
The invention belongs to the technical field of harmless treatment and utilization of nickel-containing iron slag solid waste generated in a nickel-cobalt smelting process, and particularly relates to a harmless treatment method of nickel-containing iron slag solid waste.
Background
The quantity of iron-removing tailings produced in the nickel-cobalt hydrometallurgy process every year is large, and most iron slags contain valuable metals such As Ni and Co and heavy metals such As Pb, Zn and As. The slag is returned to the pyrogenic process again to smelt and recover valuable metals in the slag, but the smelting energy consumption and the production cost are increased, and the direct recovery rate of the main nickel-cobalt metal is low; meanwhile, the continuous circulation of the tailings can also lead to the enrichment of impurity elements such As Pb, As and the like in the system, and influence is caused on the subsequent production process. And the iron-removing tailings contain harmful elements such As Pb, As and the like, belong to solid waste residues and cannot be directly buried. At present, a nickel-cobalt smelting plant can build a slag yard nearby to pile up the slag, land resources are occupied, and heavy metals in the nickel-iron slag can be continuously dissolved out under the natural piling condition to pollute underground water and soil and cause environmental pollution. Therefore, how to treat the ferronickel slag produced in the nickel-cobalt hydrometallurgy is a problem to be solved urgently nowadays.
The content of valuable metals in the ferronickel slag produced in the nickel-cobalt wet smelting process is 1.5-3.0% of Ni, 0.02-0.060% of Co0.8-2.0% of Cu, 0.5-2.5% of harmful elements As, 0.16-0.2% of Pb and 20-50% of main metal iron. The traditional process for treating the nickel-containing iron slag generally adopts a pyrogenic process or a wet process. The pyrometallurgical process is to return the slag to a pyrometallurgical system for smelting, so that iron enters the pyrometallurgical iron slag, harmful elements such as arsenic and lead enter flue gas for separation, valuable metals such as nickel and copper can enter nickel matte and the like, but the process has the problems of low recovery rate of the valuable metals, high energy consumption and cost, and environmental pollution caused by the flue gas and the like. In the wet process, valuable metals of nickel, copper and cobalt are recycled firstly, arsenic is separated, and the separation of the valuable metals, the arsenic and the iron is realized, and leaching, organic solvent extraction and other methods can be adopted in the process, but the process has the problems of high purification difficulty of leachate, high operation cost and the like. In addition, the traditional method is adopted to treat the nickel-containing iron slag solid waste, a large amount of solid slag can still be obtained, the partial slag is generally applied to places such as tailing dams and the like, land resources are continuously occupied, and environmental pollution can be caused to different degrees.
Disclosure of Invention
Aiming at the problems that a large amount of iron-removing tailings produced in the nickel-cobalt hydrometallurgy process occupy land resources and cause valuable metal loss and heavy metal pollution to the environment, the invention provides the harmless treatment method for the solid waste of the nickel-containing iron slag, which has the advantages of simple process, low treatment cost, resource utilization of the iron slag, no toxicity and no harm.
The invention adopts the following technical scheme:
a harmless treatment method for solid waste of nickel-containing iron slag is characterized by comprising the following steps:
(1) carrying out countercurrent leaching on the nickel-iron-containing slag solid waste by using a weakly acidic aqueous solution with the pH value of 2.0-3.0 to obtain acid leaching slag;
(2) adding an acid leaching residue into an alkaline solution, stirring, adjusting the pH value to 6-8, and then adding an oxidant for oxidation to obtain oxidized alkaline washing residue;
(3) adding water and a calcification agent into the oxidized alkaline washing slag, stirring and calcification for 15min-30min, adding a coagulant, continuously stirring for 10min-15min, adding cement, and stirring for 30min-60min to obtain a cementing material; pressing the cementing material into blocks, and then placing the blocks in the shade and dry place for curing for 10 to 15 days to obtain primary curing slag; the mass ratio of the oxidized alkaline washing slag, the calcification agent, the cement and the coagulant is (0.4-0.6): (0.1-0.2): (0.3-0.5): (0.05-0.1), and the water-cement ratio is 0.45-0.50;
(4) crushing the primary solidified slag into particles with the particle size smaller than 3mm, adding water, cement and sand, stirring for 30-60 min, repeating the process of preparing the cementing material in the step (3), performing secondary solidification, pressing the cementing material obtained before the secondary solidification into blocks, and placing the blocks in the open air in a cool and dry place for curing for 30-35 days to obtain secondary solidified slag; the mass ratio of the primary solidified slag to the cement to the sand is (0.3-0.4) to (0.5-0.6) to (0.05-0.1), and the water-cement ratio is 0.45-0.50;
(5) and (4) carrying out toxicity detection and strength detection on the secondary solidified slag, crushing the secondary solidified slag until the granularity is less than 10mm, and then filling the mine.
The method for the harmless treatment of the nickel-containing iron slag solid waste is characterized in that the nickel-containing iron slag solid waste comprises the following components in percentage by mass: 1.5 to 3.0 percent of Ni, 0.02 to 0.060 percent of Co, 0.8 to 2.0 percent of Cu, 0.5 to 2.5 percent of As, 0.16 to 0.2 percent of Pb and 20 to 50 percent of Fe.
The method for the harmless treatment of the nickel-containing iron slag solid waste is characterized in that the liquid-solid ratio of the weak acidic aqueous solution to the nickel-containing iron slag solid waste in the step (1) is (3-5): 1; and (3) carrying out 3-5 grade countercurrent leaching on the nickel-containing iron slag solid waste by using a weak acid aqueous solution, wherein the leaching time is 30-120 min.
The method for harmless treatment of the solid waste of the nickel-containing iron slag is characterized in that in the step (2), the mass percentage concentration of the alkaline solution is 5-10%, and the solute in the alkaline solution is one or more of sodium hydroxide, potassium hydroxide and sodium carbonate; in the step (2), the oxidant is one or more of sodium hypochlorite, sodium chlorate and hydrogen peroxide.
The method for harmless treatment of the solid waste of the nickel-containing iron slag is characterized in that in the step (3), the calcification agent is one or more of calcium carbonate, calcium oxide and calcium hydroxide; the coagulant is one or more of water glass, polyacrylamide, polymeric ferric sulfate and polymeric ferric chloride; the cement is portland cement.
The method for harmless treatment of the solid waste of the nickel-containing iron slag is characterized in that the cement added into the crushed primary solidified slag in the step (4) is portland cement, and the sand is natural sand with the granularity of less than 5 mm.
The method for harmless treatment of the solid waste of the nickel-containing iron slag is characterized in that in the step (5), the secondary solidified slag is crushed to the granularity of less than 10mm and then replaces part of rod frosting to be used as filling aggregate to fill the mine, the proportion of the secondary solidified slag replacing the rod frosting is 20-30%, and the mass concentration of the secondary solidified slag during filling is 75-80%.
The method for the harmless treatment of the solid waste of the nickel-containing iron slag is characterized in that in the step (5), As in the water leaching solution of the secondary solidified slag is less than 2.5mg/L, Ni and less than 15mg/L, Cu and less than 75mg/L, and the strength of the secondary solidified slag is more than 5 MPa.
The invention has the beneficial technical effects that: aiming at the problems of nickel-containing iron slag solid waste material treatment generated in the existing nickel-cobalt wet smelting process, the invention recycles valuable metals in the nickel-containing iron slag solid waste accumulated for a long time through the coordination of multiple process steps of countercurrent washing, alkaline oxidation, twice solidification and mine filling so as to improve the metal recovery rate in the nickel-cobalt-copper smelting process, and recycles harmful elements in the slag to the nature after harmless treatment, the solid waste slag can be used for mine filling after treatment, the exploitation cost of nickel sulfide ore is saved, limited land resources are not required to be wasted for landfill, not only the land resources are saved, but also a large amount of mine filling materials are provided, and a large amount of waste iron slag is effectively utilized as resources, thus the method is an environment-friendly method for treating the nickel-containing iron slag. The method has simple process and strong operability, and truly realizes the harmless treatment of the solid waste of the nickel-containing iron slag.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
Referring to fig. 1, the method for harmless treatment of solid waste of nickel-containing iron slag of the present invention comprises the following steps:
(1) and (3) carrying out 3-5 grade countercurrent leaching on the solid waste of the nickel-containing iron slag by using a weakly acidic aqueous solution with the pH value of 2.0-3.0, so that the content of valuable metals in the solid waste of the nickel-containing iron slag is reduced to 0.25% of Ni, 0.003% of Co and 1.05% of Cu or below. The liquid-solid ratio of the weakly acidic aqueous solution to the solid waste of the nickel-iron-containing slag is (3-5): 1, and the leaching time is 30-120 min, so that the acid leaching slag is obtained. The nickel-containing iron slag solid waste is solid waste accumulated for a long time in the nickel-cobalt hydrometallurgy process, and the nickel-containing iron slag solid waste comprises the following components in percentage by mass: 1.5 to 3.0 percent of Ni, 0.02 to 0.060 percent of Co0.02 to 0.060 percent of Cu, 0.8 to 2.0 percent of As, 0.5 to 2.5 percent of Pb, and 20 to 50 percent of Fe.
(2) Adding 5-10 wt% of alkaline solution into the acid leaching residue, stirring, adjusting the pH value to 6-8, and adding an oxidant for oxidation to obtain oxidized alkaline washing residue; the solute in the alkaline solution is one or more of sodium hydroxide, potassium hydroxide and sodium carbonate; the oxidant is one or more of sodium hypochlorite, sodium chlorate and hydrogen peroxide.
(3) Adding the oxidized alkaline washing slag into a slurry stirrer, adding water and a calcification agent, stirring for calcification for 15min-30min, adding a coagulant, continuously stirring for 10min-15min, adding cement, and stirring for 30min-60min, so that the slag is coagulated into an integral gelled material; the calcification agent is one or more of calcium carbonate, calcium oxide and calcium hydroxide; the coagulant is one or more of water glass, polyacrylamide, polymeric ferric sulfate and polymeric ferric chloride; the cement is ordinary portland cement. Pressing the cementing material into blocks by a brick making machine, and then placing the blocks in a shady and dry place for curing for 10 to 15 days in the open air to obtain primary curing slag; the mass ratio of the oxidized alkaline washing slag, the calcification agent, the cement and the coagulant is (0.4-0.6): (0.1-0.2): (0.3-0.5): (0.05-0.1), and the water-cement ratio is 0.45-0.50.
(4) Crushing the primary solidified slag into particles with the particle size smaller than 3mm, adding water, cement and sand, stirring for 30-60 min, repeating the process of preparing the cementing material in the step (3), performing secondary solidification, pressing the cementing material obtained before the secondary solidification into blocks, and placing the blocks in the open air in a cool and dry place for curing for 30-35 days to obtain secondary solidified slag; the mass ratio of the primary solidified slag to the cement to the sand is (0.3-0.4) to (0.5-0.6) to (0.05-0.1), and the water-cement ratio is 0.45-0.50; the cement added into the crushed primary solidified slag is ordinary portland cement, and the sand is natural sand with the granularity smaller than 5 mm. The nickel-containing iron slag solid waste is solidified after alkaline oxidation by adopting a twice solidification process, so that the solidification degree of heavy metal in the solidified slag and the compressive strength of the solidified slag are ensured.
(5) And (3) carrying out toxicity detection and strength detection on the secondary solidified slag, wherein the toxicity detection of the secondary solidified slag requires that As in a water extract of the secondary solidified slag is less than 2.5mg/L, Ni and less than 15mg/L, Cu and less than 75mg/L, and the strength detection of the secondary solidified slag requires that the strength of the secondary solidified slag is more than 5 Mpa. And crushing the secondary solidified slag until the granularity is less than 10mm, and then filling the mine. And crushing the secondary solidified slag to the granularity of less than 10mm, and replacing part of rod ground sand to be used as filling aggregate for mine filling, so that the resource utilization of the solid waste slag is realized. The proportion of the secondary solidified slag replacing rod frosting is 20-30%, and the mass concentration of the secondary solidified slag during filling is 75-80%.
Example 1
Taking 10kg of nickel-containing iron slag solid waste stored in a certain nickel factory slag yard for a long time, wherein the nickel-containing iron slag solid waste comprises the following components in percentage by mass: contains Ni 2.320%, Co 0.06%, Cu 1.400%, Fe 23.780%, As 1.65% and Pb 0.18%.
At normal temperature, performing 3-stage countercurrent leaching on the nickel-containing iron slag solid waste by using a weakly acidic aqueous solution with the pH value of 2.0, wherein the liquid-solid ratio of the weakly acidic aqueous solution to the nickel-containing iron slag solid waste is 3:1, and the leaching time is 30min, so as to obtain acid leaching slag. The acid leaching slag contains 0.24% of Ni, 0.003% of Co, 1.03% of Cu, 23.98% of Fe, 1.78% of As and 0.2% of Pb.
Adding 5 mass percent sodium hydroxide solution into the acid leaching residue, stirring, adjusting the pH value to 7.5, and then adding 0.5kg hydrogen peroxide for oxidation to obtain oxidized alkaline washing residue.
And adding the oxidized alkaline washing slag into a slurry stirrer, adding 13L of water, adding 2.5kg of quicklime, uniformly stirring, calcification for 30min, adding 1kg of polymeric ferric sulfate, 0.8kg of water glass and 1.4g of polyacrylamide, fully stirring for 10min, adding 8kg of cement, and stirring for 45min to obtain the cementing material. And pressing the cementing material into blocks by a brick making machine, and then placing the blocks in a shady and dry place for curing for 10 days to obtain primary curing slag.
Crushing the primary solidified slag into particles with the particle size smaller than 3mm, adding water, cement and sand, stirring for 30min, repeating the process for preparing the cementing material, performing secondary solidification, pressing the cementing material obtained before the secondary solidification into blocks, and then placing the blocks in the open air in a cool and dry place for curing for 35 days to obtain secondary solidified slag; the mass of the primary solidified slag, the mass of the cement and the mass of the sand are respectively 20kg, 34kg and 3kg, and the mass of the water is 26L.
And (3) carrying out strength detection and toxicity detection on the secondary solidified slag, wherein the compressive strength is 11.15Mp, the secondary solidified slag meets the strength requirement, and the secondary solidified slag is subjected to water immersion test, so that the leachate contains 0.22mg/L of Ni, 0.120mg/L of Cu, 0.167mg/L of Fe, 0.1mg/L of Pb and 0.5mg/L of As, and meets the national standard.
And crushing the secondary solidified slag to the granularity of less than 10mm, replacing part of rod frosting as filling aggregate, and filling the mine, wherein the proportion of the secondary solidified slag replacing the rod frosting is 30%, and the mass concentration of the secondary solidified slag during filling is 77%.
Example 2
Taking 20kg of nickel-containing iron slag solid waste stored in a certain nickel factory slag yard for a long time, wherein the nickel-containing iron slag solid waste comprises the following components in percentage by mass: 1.52% of Ni, 0.06% of Co, 0.92% of Cu, 45% of Fe, 0.55% of As and 0.17% of Pb.
At normal temperature, performing 4-stage countercurrent leaching on the nickel-containing iron slag solid waste by using a weakly acidic aqueous solution with the pH value of 2.0, wherein the liquid-solid ratio of the weakly acidic aqueous solution to the nickel-containing iron slag solid waste is 3:1, and the leaching time is 30min, so as to obtain acid leaching slag. The acid leaching slag contains 0.23% of Ni, 0.003% of Co, 0.82% of Cu, 41.58% of Fe, 0.68% of As and 0.19% of PbO.
Adding 8 mass percent sodium hydroxide solution into the acid leaching residue, stirring, adjusting the pH value to 7.5, and then adding 1.0kg hydrogen peroxide for oxidation to obtain oxidized alkaline washing residue.
Adding the oxidized alkaline washing slag into a slurry stirrer, adding 25L of water, adding 5kg of quicklime, uniformly stirring, calcifying for 30min, adding 2kg of PFS, 1.6kg of water glass and 2.8g of PAM, fully stirring for 15min, adding 15kg of cement, and stirring for 45min to obtain the cementing material. And pressing the cementing material into blocks by a brick making machine, and then placing the blocks in a shady and dry place for curing for 12 days to obtain primary curing slag.
Crushing the primary solidified slag into particles with the particle size smaller than 3mm, adding water, cement and sand, stirring for 45min, repeating the process for preparing the cementing material, performing secondary solidification, pressing the cementing material obtained before the secondary solidification into blocks, and then placing the blocks in the open air in a cool and dry place for curing for 33 days to obtain secondary solidified slag; the mass of the primary solidified slag, the mass of the cement and the mass of the sand are respectively 40kg, 55kg and 5kg, and the mass of the water is 50L.
And (3) performing strength detection and toxicity detection on the secondary solidified slag, wherein the compressive strength is 11.25Mp, the secondary solidified slag meets the strength requirement, and the secondary solidified slag is subjected to a water immersion test, so that the leachate contains 0.145mg/L of Ni, 0.03mg/L of Co, 0.092mg/L of Cu, 0.161mg/L of Fe, 0.1mg/L of Pb and 0.5mg/L of As, and meets the national standard.
And crushing the secondary solidified slag to the granularity of less than 10mm, replacing part of rod frosting as filling aggregate, and filling the mine, wherein the proportion of the secondary solidified slag replacing the rod frosting is 25%, and the mass concentration of the secondary solidified slag during filling is 78%.
Example 3
30kg of nickel-containing iron slag solid waste which is stockpiled in a certain nickel factory slag yard for a long time is taken, and the nickel-containing iron slag solid waste comprises the following components in percentage by mass: contains Ni 3.43%, Co 0.03%, Cu 2.04%, Fe 20.82%, As 2.1% and Pb 0.19%.
At normal temperature, performing 5-stage countercurrent leaching on the nickel-containing iron slag solid waste by using a weakly acidic aqueous solution with the pH value of 2.0, wherein the liquid-solid ratio of the weakly acidic aqueous solution to the nickel-containing iron slag solid waste is 3:1, and the leaching time is 30min, so as to obtain acid leaching slag. The acid leaching slag contains 0.23% of Ni, 0.002% of Co, 1.05% of Cu, 26.50% of Fe, 2.44% of As and 0.2% of Pb.
Adding 10% sodium hydroxide solution by mass into the acid leaching residue, stirring, adjusting the pH value to 7.5, and then adding 1.5kg hydrogen peroxide for oxidation to obtain oxidized alkaline washing residue.
And adding the oxidized alkaline washing slag into a slurry stirrer, adding 38L of water, adding 10kg of quicklime, uniformly stirring, calcification for 30min, adding 3kg of PFS, 2.3kg of water glass and 4.2g of PAM, fully stirring for 15min, adding 28kg of cement, and stirring for 60min to obtain the cementing material. And pressing the cementing material into blocks by a brick making machine, and then placing the blocks in a shady and dry place for curing for 15 days to obtain primary curing slag.
Crushing the primary solidified slag into particles with the particle size smaller than 3mm, adding water, cement and sand, stirring for 60min, repeating the process for preparing the cementing material, performing secondary solidification, pressing the cementing material obtained before the secondary solidification into blocks, and then placing the blocks in the open air in a cool and dry place for curing for 35 days to obtain secondary solidified slag; the mass of the primary solidified slag, the mass of the cement and the mass of the sand are respectively 60kg, 130kg and 10kg, and the mass of the water is 95L.
And (3) carrying out strength detection and toxicity detection on the secondary solidified slag, wherein the compressive strength is 11.15Mp, the secondary solidified slag meets the strength requirement, and the secondary solidified slag is subjected to water immersion test, so that the leachate contains 0.053mg/L of Ni, no Co is detected, 0.048mg/L of Cu, 0.11mg/L of Fe, 0.1mg/L of Pb and 0.5mg/L of As, and meets the national standard.
And crushing the secondary solidified slag to the granularity of less than 10mm, replacing part of rod frosting as filling aggregate, and filling the mine, wherein the proportion of the secondary solidified slag replacing the rod frosting is 20%, and the mass concentration of the secondary solidified slag during filling is 76%.
Claims (8)
1. A harmless treatment method for solid waste of nickel-containing iron slag is characterized by comprising the following steps:
(1) carrying out countercurrent leaching on the nickel-iron-containing slag solid waste by using a weakly acidic aqueous solution with the pH value of 2.0-3.0 to obtain acid leaching slag;
(2) adding an acid leaching residue into an alkaline solution, stirring, adjusting the pH value to 6-8, and then adding an oxidant for oxidation to obtain oxidized alkaline washing residue;
(3) adding water and a calcification agent into the oxidized alkaline washing slag, stirring and calcification for 15min-30min, adding a coagulant, continuously stirring for 10min-15min, adding cement, and stirring for 30min-60min to obtain a cementing material; pressing the cementing material into blocks, and then placing the blocks in the shade and dry place for curing for 10 to 15 days to obtain primary curing slag; the mass ratio of the oxidized alkaline washing slag, the calcification agent, the cement and the coagulant is (0.4-0.6): (0.1-0.2): (0.3-0.5): (0.05-0.1), and the water-cement ratio is 0.45-0.50;
(4) crushing the primary solidified slag into particles with the particle size smaller than 3mm, adding water, cement and sand, stirring for 30-60 min, repeating the process of preparing the cementing material in the step (3), performing secondary solidification, pressing the cementing material obtained before the secondary solidification into blocks, and placing the blocks in the open air in a cool and dry place for curing for 30-35 days to obtain secondary solidified slag; the mass ratio of the primary solidified slag to the cement to the sand is (0.3-0.4) to (0.5-0.6) to (0.05-0.1), and the water-cement ratio is 0.45-0.50;
(5) and (4) carrying out toxicity detection and strength detection on the secondary solidified slag, crushing the secondary solidified slag until the granularity is less than 10mm, and then filling the mine.
2. The method for the harmless treatment of the nickel-containing iron slag solid waste according to claim 1, wherein the nickel-containing iron slag solid waste comprises the following components in percentage by mass: 1.5 to 3.0 percent of Ni, 0.02 to 0.060 percent of Co, 0.8 to 2.0 percent of Cu, 0.5 to 2.5 percent of As, 0.16 to 0.2 percent of Pb and 20 to 50 percent of Fe.
3. The method for the harmless treatment of the nickel-containing iron slag solid waste according to claim 2, wherein the liquid-solid ratio of the weakly acidic aqueous solution to the nickel-containing iron slag solid waste in the step (1) is (3-5): 1; and (3) carrying out 3-5 grade countercurrent leaching on the nickel-containing iron slag solid waste by using a weak acid aqueous solution, wherein the leaching time is 30-120 min.
4. The method for harmless treatment of the solid waste of the nickel-containing iron slag according to claim 1, wherein the mass percentage concentration of the alkaline solution in the step (2) is 5% -10%, and the solute in the alkaline solution is one or more of sodium hydroxide, potassium hydroxide and sodium carbonate; in the step (2), the oxidant is one or more of sodium hypochlorite, sodium chlorate and hydrogen peroxide.
5. The method for harmless treatment of solid waste containing nickel and iron slag according to claim 1, wherein in the step (3), the calcification agent is one or more of calcium carbonate, calcium oxide and calcium hydroxide; the coagulant is one or more of water glass, polyacrylamide, polymeric ferric sulfate and polymeric ferric chloride; the cement is portland cement.
6. The method for harmless treatment of solid waste containing nickel and iron slag according to claim 1, wherein the cement added to the crushed primary solidified slag in the step (4) is portland cement, and the sand is natural sand having a particle size of less than 5 mm.
7. The method for harmless treatment of solid waste of nickel-containing iron slag according to claim 1, wherein in the step (5), the secondary solidified slag is crushed to a particle size of less than 10mm and then used as a filling aggregate to replace part of rod frosting for mine filling, the proportion of the secondary solidified slag replacing the rod frosting is 20-30%, and the mass concentration of the secondary solidified slag during filling is 75-80%.
8. The method for the harmless treatment of the solid waste of the nickel-containing iron slag according to claim 1, wherein in the step (5), As in the water leaching solution of the secondary solidified slag is less than 2.5mg/L, Ni and less than 15mg/L, Cu and less than 75mg/L, and the strength of the secondary solidified slag is more than 5 MPa.
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