CN111013080B - Method for harmless treatment of phosphate ore dressing tailing slag - Google Patents

Method for harmless treatment of phosphate ore dressing tailing slag Download PDF

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CN111013080B
CN111013080B CN201911393505.8A CN201911393505A CN111013080B CN 111013080 B CN111013080 B CN 111013080B CN 201911393505 A CN201911393505 A CN 201911393505A CN 111013080 B CN111013080 B CN 111013080B
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tailing slag
water
slag
precipitation reaction
ore dressing
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CN111013080A (en
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张延顺
朱通燃
刘璐
文昱舜
游龙江
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Guizhou Haohua Engineering Technology Co ltd
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40—Inorganic substances
    • A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40—Inorganic substances
    • A62D2101/45—Inorganic substances containing nitrogen or phosphorus
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40—Inorganic substances
    • A62D2101/49—Inorganic substances containing halogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/04—Combined processes involving two or more non-distinct steps covered by groups A62D3/10 - A62D3/40

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  • Business, Economics & Management (AREA)
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  • Processing Of Solid Wastes (AREA)

Abstract

The invention belongs to the technical field of waste treatment, and particularly relates to a method for harmlessly treating phosphate ore dressing tailing slag. The invention provides a method for harmless treatment of phosphorite beneficiation tailing slag, which comprises the following steps: mixing the phosphorite beneficiation tailing slag, the first part of water, an arsenic removal agent and a flocculating agent, and sequentially carrying out first precipitation reaction and first filtration to obtain first filter residue; and mixing the first filter residue, the second part of water and lime milk, and sequentially carrying out second precipitation reaction and second filtration to obtain harmless tailing slag. Experimental data show that the harmless tailing slag obtained by the method for harmlessly treating the phosphorite beneficiation tailing slag has the toxicity leaching detection results of fluoride of less than 10mg/L, total phosphorus of less than 0.5mg/L, total arsenic of less than 0.5mg/L and total mercury of less than 0.05mg/L, the content of toxic and harmful substances is greatly reduced, and the requirements of general industrial solid waste I-type slag are met.

Description

Method for harmless treatment of phosphate ore dressing tailing slag
Technical Field
The invention belongs to the technical field of waste treatment, and particularly relates to a method for harmlessly treating phosphate ore dressing tailing slag.
Background
The phosphorite mainly comprises middle-low grade phosphorite, and the storage amount of the phosphorite (rich ore) which can be directly processed and utilized is relatively low, and P in the phosphorite2O5The average content is about 17 percent, and most of phosphorite can not meet the quality requirement of raw material ore and can be used only after mineral separation and enrichment. Normally, for every 1t of phosphate concentrate produced, 0.44t of tailings, containing P, will be produced2O5Generally 7% to 12%, since P2O5The content is low, the limit of the current technology is met, the comprehensive utilization rate of the phosphate tailings is low, the comprehensive utilization rate is only 7%, and a large amount of phosphate tailings generated by phosphate ore dressing are mostly treated in a mode of establishing a tailing pond for stockpiling. The phosphorite tailing slag generated by mineral separation contains harmful substances such as partially soluble phosphorus, fluorine, arsenic, mercury and the like, and can be transferred and permeated into water and soil to cause environmental pollution in the daily placement process, so that water eutrophication, soil degradation and tailing powder dust diffusion can cause peripheral environmental pollution, the phosphorus tailing slag accumulated in a tailing pond must be subjected to anti-seepage treatment, and the collected percolate is effectively treated to buildThe setting and operating cost is high, and certain safety environmental risks exist.
Although some schemes for utilizing the phosphate ore dressing tailings exist at present, such as utilizing the phosphate tailings to prepare a filler to fill a mine goaf, producing a phosphate-containing fertilizer, utilizing the phosphate tailings to prepare a building material, utilizing the phosphate tailings to prepare microcrystalline glass and the like, the utilization amount of the phosphate ore dressing tailings by the above schemes is still small and cannot far keep pace with the generation speed of the phosphate ore dressing tailings, so that a large amount of phosphate ore dressing tailings still need to be stockpiled by adopting a tailing pond building mode, and the environmental problem of the current accumulation of a large amount of phosphate ore dressing tailings cannot be fundamentally solved and alleviated.
Therefore, the phosphorite beneficiation tailing slag is subjected to harmless treatment from the source, harmful substances in the phosphorite beneficiation tailing slag are removed or fixed, the transfer of harmful factors in the stacking process of the phosphorite beneficiation tailing slag is reduced, the most effective way for solving the problem of environmental safety risk caused by the stacking of a large amount of phosphorite beneficiation tailing slag at present is provided, the resource utilization of the phosphorite beneficiation tailing slag can be guaranteed while the environmental hazard is eliminated, and the method has important environmental significance and economic value.
Disclosure of Invention
In view of the above, the invention aims to provide a method for harmless treatment of phosphate ore dressing tailings, which can rapidly treat phosphate ore dressing tailings belonging to general industrial solid waste type II slag into general industrial solid waste type I slag in large batch, and is beneficial to the environment; the tailing slag treated by the method can be directly stockpiled without paving an impermeable membrane and building a special tailing pond, so that the cost is saved, and the treated tailing slag can be directly filled into places such as pits for land reclamation and can also be used as a building material raw material for comprehensive utilization.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
a method for harmless treatment of phosphate ore dressing tailing slag comprises the following steps:
mixing the phosphorite beneficiation tailing slag, the first part of water, an arsenic removal agent and a flocculating agent, and sequentially carrying out first precipitation reaction and first filtration to obtain first filter residue;
and mixing the first filter residue, the second part of water and lime milk, and sequentially carrying out second precipitation reaction and second filtration to obtain harmless tailing slag.
Preferably, the mass ratio of the phosphorite beneficiation tailing slag to the first part of water is 1: (1.5-4).
Preferably, the arsenic removing agent is one or more of sodium sulfide, sodium hydrosulfide, iron sulfide and barium sulfide; the mass of the arsenic removing agent is 0-5 times of that of arsenic in the phosphorite beneficiation tailing slag; the flocculating agent is one or more of polyaluminium chloride, polyaluminium sulfate, polyferric sulfate and aluminum ferric sulfate; the dosage of the flocculating agent is 0.01-0.1% of the total mass of the phosphorite ore dressing tailing slag and the first part of water.
Preferably, the time of the first precipitation reaction is 15-50 min.
Preferably, the mass ratio of the first filter residue to the second part of water is 1: (0.3 to 1).
Preferably, the pH value of the second precipitation reaction is 9.5-12; the dosage of the lime milk is subject to the condition of ensuring that the pH value of the second precipitation reaction is 9.5-12.
Preferably, the time of the second precipitation reaction is 5-20 min.
Preferably, the method for treating the filtrate obtained by the first filtration and the second filtration independently comprises the following steps:
mixing the filtrate with lime cream, and carrying out precipitation reaction to obtain a solid-liquid mixed system;
mixing the solid-liquid mixed system with an organic flocculant, and sequentially carrying out flocculation reaction and filtration to obtain water treatment slag and supernatant;
and the supernatant is returned to be used as water for phosphate ore dressing or water for harmless treatment of phosphate ore dressing tailing slag.
Preferably, the pH value of the precipitation reaction is 9-11.5; the dosage of the lime milk is subject to the condition that the pH value of the precipitation reaction is 9-11.5.
Preferably, the organic flocculant is one or more of polyacrylamide, polyacrylic acid and sodium polyacrylate; the dosage of the organic flocculant is 0.001-0.05% of the mass of the liquid in the solid-liquid mixed system.
The invention provides a method for harmless treatment of phosphorite beneficiation tailing slag, which comprises the following steps: mixing the phosphorite beneficiation tailing slag, the first part of water, an arsenic removal agent and a flocculating agent, and sequentially carrying out first precipitation reaction and first filtration to obtain first filter residue; and mixing the first filter residue, the second part of water and lime milk, and sequentially carrying out second precipitation reaction and second filtration to obtain harmless tailing slag. Arsenic and mercury in the phosphorite beneficiation tailing slag are fixed through the arsenic removal agent; by adding lime milk, the phosphorus, fluorine and arsenic remaining in the second filter residue react to generate insoluble solid salt, so that the content of harmful substances in the second filter residue is further reduced, and the harmless tailing slag obtained after treatment cannot cause environmental pollution due to the transfer of the harmful substances in the stacking process.
Experimental data show that the harmless tailing slag obtained by the method for harmlessly treating the phosphorite beneficiation tailing slag has the toxicity leaching detection results that fluoride is less than 10mg/L, total phosphorus is less than 0.5mg/L, total arsenic is less than 0.5mg/L, total mercury is less than 0.05mg/L, and the content of toxic and harmful substances is greatly reduced; the water quality of the treated supernatant is fluoride less than 10mg/L, total phosphorus less than 1.0mg/L, total arsenic less than 0.5mg/L and total mercury less than 0.05mg/L, the water quality is good, and the requirement of the system for process water can be met.
Detailed Description
The invention provides a method for harmlessly treating phosphorite treatment tailing slag, which comprises the following steps:
mixing the phosphorite beneficiation tailing slag, the first part of water, an arsenic removal agent and a flocculating agent, and sequentially carrying out first precipitation reaction and first filtration to obtain first filter residue;
and mixing the first filter residue, the second part of water and lime milk, and sequentially carrying out second precipitation reaction and second filtration to obtain harmless tailing slag.
In the present invention, the components are commercially available products well known to those skilled in the art, unless otherwise specified.
The method comprises the steps of mixing the phosphorite beneficiation tailing slag, the first part of water, the arsenic removal agent and the flocculating agent, and sequentially carrying out first precipitation reaction and first filtration to obtain first filter residue.
The phosphorite beneficiation tailing slag is preferably mixed with the first part of water by stirring and then mixed with the arsenic removal agent and the flocculating agent. In the invention, the phosphorite beneficiation tailing slag is preferably phosphorite beneficiation tailing slurry discharged by a wet method, and is filtered to obtain one or more of solid slag, dry tailing slag discharged by dry phosphorite beneficiation, wet tailing slag discharged by dry phosphorite beneficiation, dry tailing slag piled in a tailing pond and wet tailing slag piled in the tailing pond. In the invention, when the phosphorite beneficiation tailing slag is derived from phosphorite beneficiation tailing pulp, filtrate obtained by filtering the phosphorite beneficiation tailing pulp is preferably collected and reused in a phosphorite beneficiation system. In the invention, the mass ratio of the phosphorite beneficiation tailing slag to the first part of water is preferably 1: (1.5-4), more preferably 1: (2-3.5), and more preferably 1: (2.5-3). In the present invention, the arsenic removing agent is preferably one or more of sodium sulfide, sodium hydrosulfide, iron sulfide and barium sulfide. In the invention, the mass of the arsenic removing agent is preferably 0.3-5 times, more preferably 0.5-4.7 times, and even more preferably 1-4.5 times of the mass of arsenic in the phosphorite beneficiation tailing slag. In the invention, the arsenic removal agent can react a part of arsenic in the phosphorite beneficiation tailing slag to generate insoluble salt, thereby realizing the fixation of arsenic and reducing the harm of arsenic to the environment.
In the present invention, the flocculant is preferably one or more of polyaluminium chloride, polyaluminium sulfate, polyferric sulfate and aluminum ferric sulfate. In the invention, the dosage of the flocculating agent is preferably 0.01-0.1%, more preferably 0.03-0.08%, and even more preferably 0.04-0.06% of the total mass of the phosphorite beneficiation tailing slag and the first part of water. The flocculating agent is added, so that the agglomeration of the ore pulp and the first precipitation reaction product particles is increased, and the slag-water separation of the subsequent first filtration is facilitated.
In the invention, the time of the first precipitation reaction is preferably 15-50 min, more preferably 20-45 min, and still more preferably 25-40 min. In the present invention, the temperature of the first precipitation reaction is preferably room temperature, specifically 18 to 25 ℃.
In the invention, the soluble arsenic in the phosphate ore dressing tailing slag is mainly inorganic arsenate (AsO)4 3-) And arsenite (AsO)3 3-) Or in the form of methylated arsenic compounds in natural water, wherein the arsenic is in the form of cations under acidic conditions, and can generate insoluble As after adding a sulfur-containing arsenic removal agent2S3Precipitating; meanwhile, sulfur in the arsenic removing agent can also react with mercury to produce mercury sulfide precipitate, so that toxic and harmful element mercury is removed.
In the present invention, the main chemical reaction formula of the first precipitation is as follows:
Figure BDA0002345650750000041
Figure BDA0002345650750000042
Figure BDA0002345650750000043
Figure BDA0002345650750000044
Figure BDA0002345650750000045
Figure BDA0002345650750000051
the first filtration mode is not particularly limited in the present invention, and may be a filtration mode known to those skilled in the art, specifically, a filter pressing mode, a vacuum filtration mode or a centrifugation mode.
The washing method of the present invention is not particularly limited, and a washing method known to those skilled in the art may be used. The invention has the advantages that through the washing,soluble phosphorus, fluorine and arsenic are dissolved in water, so that the content of the soluble phosphorus, the fluorine and the arsenic in the phosphorite beneficiation tailing slag is reduced, and the soluble arsenic is reacted to generate insoluble As by adding an arsenic removing agent2S3And precipitation can reduce the content of soluble arsenic in the obtained first filtrate, thereby being beneficial to preventing the content of arsenic in the water treatment slag from exceeding the standard.
After the first filter residue is obtained, the first filter residue, the second part of water and lime milk are mixed, and a second precipitation reaction and a second filtration are sequentially carried out to obtain harmless tailing slag.
According to the invention, preferably, the first filter residue and the second part of water are stirred and mixed into slurry, and then the slurry is mixed with lime milk. In the invention, the mass ratio of the first filter residue to the second part of water is preferably 1: (0.3 to 1), more preferably 1: (0.4 to 0.9), and more preferably 1: (0.5-0.8).
In the invention, the pH value of the second precipitation reaction is preferably 9.5-12, more preferably 9.7-11.5, and still more preferably 10-11.2. In the invention, the lime milk is preferably obtained by mixing quick lime with water or by mixing slaked lime with water. In the invention, the dosage of the lime milk is preferably determined to ensure that the pH value of the second precipitation reaction is 9.5-12.
In the invention, the time of the second precipitation reaction is preferably 5-20 min, more preferably 8-18 min, and still more preferably 10-15 min.
According to the invention, the lime milk and the first filter residue are mixed and reacted, and phosphorus, fluorine and arsenic ions remained in the first filter residue are further generated into insoluble precipitates, so that the environmental pollution caused by the transfer of phosphorus, fluorine and arsenic in the stacking process is reduced.
In the present invention, the chemical reaction formula of the second precipitation occurs as follows:
5Ca2++7OH-+3H2PO4-＝Ca5(OH)(PO4)3↓+6H2O；
Ca2++2F-＝CaF2↓；
3Ca2++2AsO4 3-＝Ca3(AsO4)2↓；
3Ca2++2AsO3 3-＝Ca3(AsO3)2↓。
in the present invention, the method for treating the filtrate obtained by the first filtration and the second filtration preferably independently comprises the steps of:
mixing the filtrate with lime cream, and carrying out precipitation reaction to obtain a solid-liquid mixed system;
mixing the solid-liquid mixed system with an organic flocculant, and sequentially carrying out flocculation reaction and filtration to obtain water treatment slag and supernatant;
and the supernatant is returned to be used as water for phosphate ore dressing or water for harmless treatment of phosphate ore dressing tailing slag.
In the invention, the pH value of the precipitation reaction is preferably 9-11.5, more preferably 9.2-11.3, and still more preferably 9.5-11. In the invention, the dosage of the lime milk is preferably based on the condition that the pH value of the precipitation reaction is 9-11.5. In the present invention, the organic flocculant is preferably one or more of Polyacrylamide (PAM), polyacrylic acid (PAA), and sodium Polyacrylate (PAAs); the dosage of the organic flocculant is preferably 0.001-0.05% of the mass of the liquid in the solid-liquid mixed system, more preferably 0.005-0.045%, and even more preferably 0.01-0.04%. In the invention, the organic flocculant can increase the volume of solid particles, shorten the settling time and improve the separation efficiency of filtered slag and water. In the invention, P, F, As ions in the filtrate react with lime milk to generate insoluble Ca5(OH)(PO4)3、CaF2Calcium arsenate or calcium arsenite is precipitated and is precipitated under the action of a flocculating agent, so that the content of phosphorus, fluorine and arsenic ions in water is reduced.
The supernatant obtained by the invention is preferably returned to be used as water for phosphate ore dressing or water for harmless treatment of phosphate ore dressing tailing slag; the obtained water treatment slag is preferably used as a phosphoric acid production raw material, as filter concentrate or white fertilizer.
The second filtration method is not particularly limited in the present invention, and may be filtration methods known to those skilled in the art, such as pressure filtration, vacuum filtration or centrifugation.
The harmless tailing slag obtained by the treatment of the method can be directly stockpiled and backfilled into a pit for land reclamation or used as a raw material for preparing building products.
In order to further illustrate the present invention, the method for the harmless treatment of the phosphate ore dressing tailings provided by the present invention is described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1500g of uniformly mixed phosphorite beneficiation tailing slurry with the solid content of 60 percent and the pH value of 6.1 is filtered to obtain 1125g of solid phosphorite beneficiation tailing slag, and filtrate is collected and returned to a beneficiation system;
1125g of phosphorite ore dressing tailing slag, 1800g of water, 0.02g of sodium sulfide and 0.8g of polyaluminium sulfate are mixed, stirred for 25min and subjected to first filtration to obtain first filtrate and first filter residue;
mixing the obtained first filter residue with 300g of water, stirring to be slurry, adding lime milk until the pH value is 12, reacting for 7min, and performing second filtration to obtain second filtrate and harmless tailing slag;
and combining the first filtrate and the second filtrate, adding lime milk, mixing until the pH value is 11, reacting for 20min, adding 20mg of organic flocculant PAM, uniformly stirring, standing, filtering, adding dilute sulfuric acid into obtained supernatant (filtrate) to adjust the pH value to 6-9, directly recycling the supernatant (filtrate) to a phosphorite ore dressing tailing slag harmless treatment system, and transporting obtained water treatment slag outwards for comprehensive utilization. The concentration of the dilute sulfuric acid is not particularly limited in the present invention, and the concentration of the dilute sulfuric acid for adjusting the pH value of the system, which is well known to those skilled in the art, may be used.
Example 2
1500g of uniformly mixed phosphorite beneficiation tailing slurry with the solid content of 60 percent and the pH value of 6.1 is filtered to obtain 1128g of solid phosphorite beneficiation tailing slag, and filtrate is collected and returned to a beneficiation system;
mixing 1128g of phosphorite beneficiation tailing slag, 1800g of water and 0.8g of polyaluminium chloride, stirring for 20min, and performing first filtration to obtain first filtrate and first filter residue;
mixing the obtained first filter residue with 300g of water, stirring to be slurry, adding lime milk until the pH value is 11.2, reacting for 8min, and then carrying out second filtration to obtain second filtrate and harmless tailing slag;
and combining the first filtrate and the second filtrate, adding lime milk, mixing until the pH value is 9.6, reacting for 27min, adding 20mg of organic flocculant PAM, uniformly stirring, standing, filtering, adding sulfuric acid into the obtained supernatant (filtrate) to adjust the pH value to 6-9, directly reusing the supernatant (filtrate) in a phosphorite ore dressing tailing slag harmless treatment system, and transporting the obtained water treatment slag outwards for comprehensive utilization.
Example 3
1500g of uniformly mixed phosphorite beneficiation tailing slurry with the solid content of 60 percent and the pH value of 6.1 is filtered to obtain 1130g of solid phosphorite beneficiation tailing slag, and filtrate is collected and returned to a beneficiation system for use;
mixing 1130g of phosphorite beneficiation tailing slag, 1800g of water, 0.03g of sodium sulfide and 0.8g of polymeric ferric sulfate, stirring for 30min, and performing first filtration to obtain a first filtrate and a first filter residue;
mixing the obtained first filter residue with 300g of water, stirring to be slurry, adding lime milk until the pH value is 10, reacting for 10min, and performing second filtration to obtain second filtrate and harmless tailing slag;
and combining the first filtrate and the second filtrate, adding lime milk, mixing until the pH value is 10.5, reacting for 10min, adding 20mg of organic flocculant PAM, uniformly stirring, standing, filtering, adding sulfuric acid into the obtained supernatant (filtrate) to adjust the pH value to 6-9, directly reusing the supernatant (filtrate) in a phosphorite ore dressing tailing slag harmless treatment system, and transporting the obtained water treatment slag outwards for comprehensive utilization.
Example 4
Mixing 1000g of phosphorite beneficiation tailing slag with the pH value of 6.8, 1800g of water, 0.03g of iron sulfide and 0.8g of polyaluminium sulfate, stirring for 25min, and performing first filtration to obtain first filtrate and first filter residue;
mixing the obtained first filter residue with 300g of water, stirring to be slurry, adding lime milk until the pH value is 10.5, reacting for 7min, and then carrying out second filtration to obtain second filtrate and harmless tailing slag;
and combining the first filtrate and the second filtrate, adding lime milk, mixing until the pH value is 10, reacting for 22min, adding 20mg of organic flocculant PAM, uniformly stirring, standing, filtering, directly recycling the obtained supernatant (filtrate) to a phosphorite beneficiation tailing slag harmless treatment system, and externally transporting the obtained water treatment slag for comprehensive treatment.
Example 5
Mixing 1000g of phosphate ore dressing tailing slag with the pH value of 6.8 with 1800g of water, 0.04g of sodium sulfide and 0.9g of polymeric ferric sulfate, stirring for 20min, and performing first filtration to obtain first filtrate and first filter residue;
mixing the obtained first filter residue with 250g of water, stirring to be slurry, adding lime milk until the pH value is 10.5, reacting for 5min, and then carrying out second filtration to obtain second filtrate and harmless tailing slag;
and combining the first filtrate and the second filtrate, adding the first filtrate and the second filtrate, mixing the first filtrate and the second filtrate with lime milk until the pH value is 10, reacting for 25min, adding 20mg of organic flocculant PAM, uniformly stirring, standing, filtering, adding sulfuric acid into obtained supernatant (filtrate) to adjust the pH value to be 6-9, directly recycling the supernatant (filtrate) to a phosphorite ore dressing tailing slag harmless treatment system, and transporting obtained water treatment slag outwards for comprehensive utilization.
Example 6
Mixing 1000g of phosphate ore dressing tailing slag with the pH value of 6.8, 1800g of water and 0.9g of polymeric ferric sulfate, stirring for 20min, and performing first filtration to obtain a first filtrate and a first filter residue;
mixing the obtained first filter residue with 250g of water, stirring to be slurry, adding lime milk until the pH value is 10.5, reacting for 5min, and then carrying out second filtration to obtain second filtrate and harmless tailing slag;
and combining the first filtrate and the second filtrate, adding lime milk, mixing until the pH value is 10.5, reacting for 25min, adding 20mg of organic flocculant PAM, uniformly stirring, standing, filtering, adding sulfuric acid into the obtained supernatant (filtrate) to adjust the pH value to 6-9, directly reusing the obtained supernatant (filtrate) in a phosphorite ore dressing tailing slag harmless treatment system, and carrying out outward comprehensive treatment on the obtained water treatment slag.
Comparative example 1
The tailing slurry of phosphorus ore dressing having a solid content of 60% and a pH of 6.1 used in example 1 was filtered, and the obtained filtrate and tailing slurry of phosphorus ore dressing were used as comparative examples.
Performing poison leaching detection on the harmless tailing slag obtained in the examples 1-6 and the directly filtered tailing slag obtained in the comparative example 1 by using water as a solvent according to a HJ 557-2010 horizontal oscillation method, wherein detection results are shown in Table 1; the supernatant obtained by the treatment of the examples 1 to 6 and the filtrate obtained by directly filtering tailing slurry in the comparative example 1 are detected, and the detection results are shown in table 2.
Table 1 examples 1-6 harmless tailing slag and comparative example 1 direct filtration tailing slag poison leaching detection results
P/(mg/L) F/(mg/L) As/(μg/L) Hg/(μg/L)
Comparative example 1 23.97 7.54 257.8 0.225
Example 1 0.05 2.89 10.76 0.172
Example 2 0.1 2.76 30.5 0.177
Example 3 0.3 3.18 13.12 0.212
Example 4 0.28 2.9 9.21 0.149
Example 5 0.46 4.71 58.10 0.149
Example 6 0.31 3.1 15.21 0.130
TABLE 2 detection results of the supernatants of examples 1-6 and the filtrate of comparative example 1
P/(mg/L) F/(mg/L) As/(μg/L) Hg/(μg/L)
Comparative example 1 244 42.61 4981 0.688
Example 1 0.55 5.86 75 0.20
Example 2 0.69 9.13 86 0.24
Example 3 0.84 6.75 78 0.31
Example 4 0.90 6.75 90 0.25
Example 5 0.91 7.25 74 0.38
Example 6 0.75 8.1 77 0.37
As can be seen from tables 1 and 2, the contents of phosphorus, fluorine, arsenic and mercury in the harmless tailing slag obtained by the treatment of the method provided by the invention are greatly reduced, and the standard of industrial solid waste type I slag can be achieved; the supernatant obtained by treatment meets the requirement of process reuse water, can be returned to a system to be continuously used as washing water for harmless treatment of the phosphorite beneficiation tailing slag or sent to a phosphorite beneficiation working section for use, does not need to be discharged outside, and cannot generate a new sewage source; in addition, the phosphorus content in the harmless tailing slag and the supernatant is greatly reduced, which indicates that the water treatment slag contains higher effective phosphorus, and the obtained water treatment slag can be further utilized as a phosphorus resource.
The method for the harmless treatment of the phosphorite beneficiation tailing slag effectively solves the problem of safe environment caused by the stockpiling of a large amount of phosphorite beneficiation tailing slag, can quickly treat the phosphorite beneficiation tailing slag belonging to general industrial solid waste type II slag into general industrial solid waste type I slag in large batch, and is beneficial to the environment; the tailing slag treated by the method can be directly stockpiled without paving an impermeable membrane and building a special tailing pond, so that the cost is saved, and the treated tailing slag can be directly filled into places such as pits for land reclamation and can also be used as a building material raw material for comprehensive utilization.
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.

Claims (9)

1. A method for harmless treatment of phosphate ore dressing tailing slag is characterized by comprising the following steps:
mixing the phosphorite beneficiation tailing slag, the first part of water, an arsenic removal agent and a flocculating agent, and sequentially carrying out first precipitation reaction and first filtration to obtain first filter residue;
mixing the first filter residue, the second part of water and lime milk, and sequentially carrying out a second precipitation reaction and a second filtration to obtain harmless tailing slag;
the pH value of the second precipitation reaction is 9.5-12; the dosage of the lime milk is subject to the condition of ensuring that the pH value of the second precipitation reaction is 9.5-12.
2. The method according to claim 1, wherein the mass ratio of the phosphate ore dressing tailing slag to the first part of water is 1: (1.5-4).
3. The method of claim 1, wherein the arsenic removal agent is one or more of sodium sulfide, sodium hydrosulfide, iron sulfide, and barium sulfide; the mass of the arsenic removing agent is 0.3-5 times of that of arsenic in the phosphorite ore dressing tailing slag; the flocculating agent is one or more of polyaluminium chloride, polyaluminium sulfate, polyferric sulfate and aluminum ferric sulfate; the dosage of the flocculating agent is 0.01-0.1% of the total mass of the phosphorite ore dressing tailing slag and the first part of water.
4. The method according to claim 1, wherein the time of the first precipitation reaction is 15 to 50 min.
5. The method according to claim 1, wherein the mass ratio of the first filter residue to the second portion of water is 1: (0.3 to 1).
6. The method according to claim 1, wherein the time of the second precipitation reaction is 5 to 20 min.
7. The method according to claim 1, wherein the method of treating the filtrates from the first and second filtration independently comprises the steps of:
mixing the filtrate with lime cream, and carrying out precipitation reaction to obtain a solid-liquid mixed system;
mixing the solid-liquid mixed system with an organic flocculant, and sequentially carrying out flocculation reaction and filtration to obtain water treatment slag and supernatant;
and the supernatant is returned to be used as water for phosphate ore dressing or water for harmless treatment of phosphate ore dressing tailing slag.
8. The method according to claim 7, wherein the precipitation reaction has a pH of 9 to 11.5; the dosage of the lime milk is subject to the condition that the pH value of the precipitation reaction is 9-11.5.
9. The method of claim 7, wherein the organic flocculant is one or more of polyacrylamide, polyacrylic acid, and sodium polyacrylate; the dosage of the organic flocculant is 0.001-0.05% of the mass of the liquid in the solid-liquid mixed system.
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