CN114505166A - Method for harmlessly transforming barium slag and recycling barium salt - Google Patents
Method for harmlessly transforming barium slag and recycling barium salt Download PDFInfo
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- CN114505166A CN114505166A CN202011275778.5A CN202011275778A CN114505166A CN 114505166 A CN114505166 A CN 114505166A CN 202011275778 A CN202011275778 A CN 202011275778A CN 114505166 A CN114505166 A CN 114505166A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/06—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
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Abstract
A method for harmlessly treating barium slag and recovering barium salt, comprising the steps of: barium slag is innocent; centrifugal separation; concentrating; performing foam flotation roughing; and (4) foam flotation and fine selection. The invention utilizes the acid water in the phosphating factory slag library to efficiently solidify the soluble barium in the barium slag, greatly reduces the concentration of harmful ions in the barium slag, and can meet the requirements of national hazardous waste landfill pollution control standard GB 18958-2001; the method has the advantages that while harmless barium slag is realized, a centrifugal mineral separation and foam flotation combined process is adopted, useful barium salt minerals in the barium slag are effectively recycled, the BaO grade in a barium concentrate dry basis is not less than 50%, the barium concentrate dry basis can be used as a raw material of barium chemical industry, efficient comprehensive utilization of resources is realized, and emission of tailings is reduced.
Description
Technical Field
The invention relates to a method for harmlessly transforming barium slag, in particular to a method for harmlessly transforming barium slag and recycling barium salt.
Background
In the production process of barium carbonate, barite and coal powder are calcined at high temperature to form barium sulfide, barium carbonate can be generated after carbon dioxide is introduced after barium sulfide is hydrolyzed, and the produced barium-containing solid waste residue is barium residue; according to the record of the national hazardous waste book 2008, barium slag is a hazardous solid waste. China is a large discharge country of barium residues, the discharge amount of the barium residues is about 100 million tons every year, harmful components in the barium residues are mainly barium ions, respiratory tracts, muscle cells, cardiovascular functions, mucous membranes and the like of human bodies are damaged, if the barium ions are directly stacked, the requirements of standard management of hazardous wastes cannot be met, a large amount of land is occupied, and the environment is influenced to be attractive. Meanwhile, in the barium salt leaching process, the utilization rate of barite is only 70-75%, a large amount of barium salt is remained in barium slag, the barite is directly discarded as waste to cause a large amount of resource waste, and meanwhile, the discharge amount of tailings is increased.
At present, the harmless treatment of the barium slag mainly removes soluble barium ions in the barium slag by adding sulfuric acid, sulfurous acid or sulfate, and simultaneously realizes the aim of detoxification by adding phosphogypsum, red mud, manganese slag, cement clinker and other substances into the barium slag.
CN 107597801A discloses a method for innocent treatment of barium slag by using phosphogypsum; the method comprises the steps of crushing, mixing and stirring the barium slag and the phosphogypsum, and precipitating and solidifying soluble barium ions in the barium slag by using acid radical ions in the phosphogypsum; CN 110681669A discloses a method for harmless treatment of barium slag by red mud; the method mixes and stirs the red mud and the barium slag, and then bakes the mixture at a low temperature to realize the harmlessness of the barium slag; CN 106734056A discloses a harmless treatment method of barium slag, which realizes the harmless treatment of barium slag by mixing and stirring the barium slag and manganese slag; although the method can realize the detoxification of barium slag, the introduced gypsum, red mud and manganese slag can greatly increase the amount of waste slag and increase the burden of a tailing pond.
CN 104496223A discloses a barium residue detoxification method; the method is characterized in that barium slag is added into cement raw materials, the cement raw materials are stirred and uniformly mixed, cement clinker is calcined through a rotary kiln, and harmlessness of the barium slag is achieved.
CN 108176700A discloses a harmless treatment method of barium slag; the method is characterized in that barium slag and sulfuric acid are quickly and fully reacted in water under the stirring condition to generate barium sulfate precipitate, and then harmless treatment is carried out in a mode of separating the barium slag by solid-liquid separation. Although the method can carry out harmless treatment on the barium slag, the barium salt can not be recycled, thereby causing resource waste.
CN 109970089 a discloses a method and a system for preparing barium sulfate by using barium slag; the invention recovers barium sulfate in barium slag by a gravity separation method. The single gravity separation efficiency is low, and the recovery effect of the fine-grained barium salt is poor.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide a method for harmlessly converting barium slag and recovering barium salt, which is simple and has high barium recovery rate.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for harmlessly treating barium slag and recovering barium salt, comprising the steps of:
(1) harmless treatment of barium slag: mixing barium slag and slag reservoir water of a phosphorization plant, performing wet grinding, and sieving to obtain ore pulp;
(2) centrifugal separation: rinsing and centrifugally separating the ore pulp obtained in the step (1) by using a centrifugal separator, wherein the separated mineral with high density is centrifugal concentrate, and the mineral with low density is centrifugal tailings;
(3) concentration: settling and concentrating the centrifugal concentrate obtained in the step (2) to obtain concentrated underflow and overflow liquid, and returning the overflow liquid to the step (2) to be used as rinsing liquid;
(4) and (3) foam flotation roughing: wet grinding and sieving the concentrated underflow obtained in the step (3) to obtain wet grinding ore pulp; placing the wet-milled ore pulp into a flotation tank, adding slag storage water of a phosphorization factory for pulp mixing, adding an inhibitor, stirring, adding a collecting agent, stirring, finally adding a foaming agent, stirring, performing air flotation, taking a product in the flotation tank as flotation tailings, and taking a flotation foam product as roughing concentrate;
(5) foam flotation and fine selection: and (4) placing the roughed concentrate obtained in the step (4) into a flotation tank, adding slag storage water of a phosphating plant for size mixing, adding an inhibitor, stirring, performing air flotation, taking the product in the flotation tank as middlings, returning to the foam flotation rougher flotation operation in the step (4), and performing flotation on the foam product to obtain a final concentrate product.
In the barium slag, the barium carbonate content is 20-25 wt%, the barium sulfate content is 8-12 wt%, the BaS content is 2.5-4.5 wt%, the carbon is 5-8 wt%, and the SiO is2The content is 20-25 wt%; in the slag storage water of the phosphating plant, the concentration of phosphate radicals is 4500-6000 mg/L, the concentration of sulfate radicals is 12000-16000 mg/L, and the pH value of the slag storage water is 1.8-2.2.
Preferably, in the step (1), the barium slag is wet-milled by a rod mill, and the mass of the mineral with the granularity of less than 0.15mm after ore milling is equal to more than 90% of the mass of the total raw ore.
Preferably, in the step (1), the mass of the water in the slag reservoir is 0.5-0.8 times of the mass of the barium slag.
Preferably, in step (2), the centrifugal concentrator is an SL type centrifugal concentrator.
Preferably, in the step (2), the concentration of the centrifugally separated feed is 10-20%, the rotating speed of a rotary drum of the centrifugal separator is 500-800 rpm, the pulp treatment capacity is 0.6-1.5 Kg/min, and the flow rate of the rinsing liquid is 0.4-1.0L/min.
Preferably, in the step (3), the concentration of the concentrated underflow is 60-64%.
Preferably, in the step (4), the concentrated underflow is subjected to wet grinding by using a rod mill, and the mass of the ore with the particle size of less than 0.074mm after wet grinding is equal to 65-75% of the mass of the total raw ore.
Preferably, in the step (4), the water in the slag storage is added to adjust the pulp until the mass concentration of the ore pulp is 25-38% and the pH value is 5.5-6.5.
Preferably, in the step (4) or the step (5), the inhibitor is water glass acidified by sulfuric acid, the mass ratio of the water glass to the sulfuric acid is 100: 1-5, and the modulus of the water glass is 2.5-3.0.
Preferably, in the step (4), the dosage of the inhibitor is 200-500 g/t; the method is used for inhibiting silicate minerals and realizing separation of the silicate minerals and barium salt minerals.
Preferably, in the step (4), the time for stirring after adding the inhibitor is 2-4 min.
Preferably, in the step (4), the collector is one or more than two of sodium palmitate, sodium myristate and sodium laurate.
Preferably, in the step (4), the amount of the collector is 100-500 g/t.
Preferably, in the step (4), the time for stirring after the collecting agent is added is 3-5 min.
Preferably, in the step (4), the foaming agent is one or more of alkyl phosphate, ethoxylated fatty acid phosphate and alkylphenol ether phosphate.
Preferably, in the step (4), the amount of the foaming agent is 50-200 g/t.
Preferably, in the step (4), the foaming agent is added and then stirred for 1-2 min.
Preferably, in the step (4), the time of the air flotation is 2-8 min.
Preferably, in the step (5), the pulp is blended until the pH value of the pulp is 5.5-6.5.
Preferably, in the step (5), the dosage of the inhibitor is 50-100 g/t.
Preferably, in the step (5), the time for stirring after adding the inhibitor is 2-5 min.
Preferably, in the step (5), the time of the air flotation is 3-5 min.
And combining the centrifugal tailings and the flotation tailings to be used as final tailings, and carrying out solution pH measurement and toxicity leaching analysis according to hazardous waste identification standard-leaching toxicity identification (GB 5085.3-2007).
The principle of the invention is as follows: the acidic water in the slag reservoir of the phosphating factory contains a large amount of sulfate radical and phosphate radical ions, and under the activation action of the mechanical force of the rod mill, soluble barium in the barium slag can be efficiently solidified, so that the soluble barium ions in the barium slag are effectively reduced, and the toxicity of the barium slag is reduced. Meanwhile, under the condition of the existence of a centrifugal force field, a part of gangue minerals are preferentially pre-thrown out by utilizing the difference of motion tracks of the barium salt minerals and the gangue minerals, the BaO grade of the barium salt minerals is improved, the difference of surface hydrophobicity of the barium salt minerals and the gangue minerals is increased by a flotation reagent, the BaO grade of the barium salt minerals is further improved by utilizing a foam flotation process, high-grade barium salt concentrate can be obtained, the barium salt concentrate can be used as a raw material of barium chemical industry, the recycling of resources is realized, and the discharge amount of barium slag is reduced.
Most of barium resources and chemical industries in China are concentrated in Guizhou areas, Guizhou areas are important phosphorization industry bases in China, and phosphorization factory slag yard water is acidic wastewater discharged in the wet-process phosphoric acid production process and is large in discharge amount. Therefore, the method has the advantage of low cost by utilizing the water in the slag reservoir to realize the detoxification of the barium slag, and simultaneously does not increase the discharge amount of the waste slag. In addition, the method of centrifugal separation and foam flotation can be used for recovering barium salt minerals in the barium slag, so that the high-efficiency utilization of resources is realized, and the emission of tailings is reduced.
The invention has the following beneficial effects:
(1) the invention utilizes the acid water in the phosphating factory slag library to efficiently solidify the soluble barium in the barium slag, greatly reduces the concentration of harmful ions in the barium slag, and can meet the requirements of national hazardous waste landfill pollution control standard GB 18958-2001;
(2) the invention realizes the harmlessness of the barium slag, simultaneously adopts the combined process of centrifugal mineral separation and froth flotation, effectively recycles the useful barium salt mineral in the barium slag, ensures that the BaO grade in the dry basis of the barium concentrate is not less than 50 percent, can be used as the raw material of barium chemical industry, realizes the high-efficiency comprehensive utilization of resources and reduces the emission of tailings.
Detailed Description
The present invention will be further described with reference to the following examples.
Unless otherwise specified, the percentages in the examples of the present invention are mass percentages.
The starting materials or chemicals used in the examples of the present invention are, unless otherwise specified, commercially available in a conventional manner.
In each example, the chemical composition of the sample was measured using an ICP instrument.
Example 1
The barium slag used in this example was a barium slag of Guizhou, containing 22% barium carbonate, 10% barium sulfate, 3.3% BaS, 5.5% carbon, and SiO2Content 22%, pH = 11.2.
In the slag storage water of the phosphorization plant used in the embodiment, the phosphate radical concentration is 5500mg/L, the sulfate radical concentration is 15000mg/L, and the pH value is = 1.9.
The acidified water glass used in this example was prepared with water glass and sulfuric acid in a mass ratio of 100: 2, and the modulus of the water glass was 2.8.
The method for harmlessly converting barium slag and recycling barium salt in the embodiment comprises the following specific steps:
(1) mixing barium slag and slag reservoir water of a phosphating plant according to the mass ratio of 10: 7, performing wet grinding, and sieving, wherein the mass of ore with the granularity of less than 0.15mm after grinding is equal to 92 percent of the total raw ore mass, so as to obtain ore pulp;
(2) rinsing and centrifugally separating the ore pulp obtained in the step (1) by using an SL type centrifugal separator, wherein the separated mineral with high density is centrifugal concentrate, and the mineral with low density is centrifugal tailings; the concentration of the centrifugal separation feeding material is 12 percent, the rotating speed of a rotary drum of the centrifugal separator is 500rpm, the ore pulp treatment capacity is 0.8Kg/min, and the flow rate of the rinsing liquid is 0.6L/min;
(3) settling and concentrating the centrifugal concentrate obtained in the step (2) to obtain concentrated underflow and overflow liquid, and returning the overflow liquid to the step (2) to be used as rinsing liquid; the concentration of the settled underflow is 64%;
(4) wet grinding and sieving the concentrated underflow obtained in the step (3), wherein the mass of the ore with the granularity of less than 0.074mm after wet grinding is equal to 65 percent of the total raw ore mass; placing wet-milled ore pulp into a flotation tank, adding slag storage water of a phosphating plant for size mixing until the mass concentration of the ore pulp is 25%, the pH value of the ore pulp is 5.5, adding acidified water glass, performing flotation on raw ore with the dosage of 200g/t, stirring for 2min, adding sodium palmitate with the dosage of 100g/t, performing flotation on the raw ore for 3min, finally adding alkyl phosphate with the dosage of 50g/t, performing flotation on the raw ore for 1min, performing inflation flotation for 5min, taking a product in the flotation tank as flotation tailings, and performing flotation on a foam product as roughing concentrate;
(5) and (3) placing the roughed concentrate obtained in the step (4) into a flotation tank, adding slag storage water of a phosphating plant for size mixing until the pH value is 5.5, adding acidified water glass, performing flotation on the raw ore with the use amount of 50g/t, stirring for 2min, performing air flotation for 3min, returning the product in the flotation tank as middling to the foam flotation rougher operation in the step (4), and performing flotation on the foam product to obtain a final concentrate product.
Through detection, the BaO content in the dry basis of the concentrate obtained in the embodiment is 55%, and the concentrate can be used as a raw material of barium chemical industry.
And combining the centrifugal tailings and the flotation tailings to be used as final tailings, and carrying out solution pH measurement and toxicity leaching analysis according to hazardous waste identification standard-leaching toxicity identification (GB 5085.3-2007). The detection result is as follows: the pH value of the final tailings is 7.5, and the concentration of barium and compounds thereof in the final tailings leaching solution is 20.5mg/L, so that the requirement of filling barium slag into a field for landfill is met.
Example 2
The barium slag used in this example was barium slag of Guizhou, which contained 20% barium carbonate, 12% barium sulfate, 3% BaS, 5% carbon, and SiO2Content 25%, pH = 11.5.
In the slag storage water of the phosphorization plant used in the embodiment, the phosphate radical concentration is 5500mg/L, the sulfate radical concentration is 15000mg/L, and the pH value is = 1.9.
The acidified water glass used in the present example was prepared from water glass and sulfuric acid in a mass ratio of 100: 3, and the modulus of the water glass was 2.7.
The method for harmlessly converting barium slag and recycling barium salt in the embodiment comprises the following specific steps:
(1) mixing barium slag and slag reservoir water of a phosphorization plant according to the mass ratio of 10: 6, performing wet grinding, and sieving, wherein the mass of minerals with the particle size of less than 0.15mm after grinding is equal to 95% of the total mass of raw ores, so as to obtain ore pulp;
(2) rinsing and centrifugally separating the ore pulp obtained in the step (1) by using an SL type centrifugal separator, wherein the separated mineral with high density is centrifugal concentrate, and the mineral with low density is centrifugal tailings; the concentration of the centrifugal separation feeding is 15%, the rotating speed of a rotary drum of the centrifugal separator is 600rpm, the ore pulp treatment capacity is 1.0Kg/min, and the flow rate of the rinsing liquid is 0.8L/min;
(3) settling and concentrating the centrifugal concentrate obtained in the step (2) to obtain concentrated underflow and overflow liquid, and returning the overflow liquid to the step (2) to be used as rinsing liquid; the concentration of the settled underflow is 64%;
(4) wet grinding and sieving the concentrated underflow obtained in the step (3), wherein the mass of the ore with the granularity of less than 0.074mm after wet grinding is equal to 70 percent of the total raw ore mass; placing wet-milled ore pulp into a flotation tank, adding slag storage water of a phosphating plant for size mixing until the mass concentration of the ore pulp is 25%, the pH value of the ore pulp is 5.5, adding acidified water glass, performing flotation on raw ore with the dosage of 300g/t, stirring for 2min, adding sodium myristate with the dosage of 200g/t, performing flotation on the raw ore for 3min, finally adding ethoxylated fatty acid phosphate with the dosage of 80g/t, performing flotation on the raw ore for 2min, performing inflation flotation for 5min, taking the product in the flotation tank as flotation tailings, and obtaining a flotation froth product as rougher concentrate;
(5) and (3) placing the roughed concentrate obtained in the step (4) into a flotation tank, adding slag storage water of a phosphating plant for size mixing until the pH value is 5.5, adding acidified water glass, performing flotation on the raw ore with the use amount of 50g/t, stirring for 2min, performing air flotation for 3min, taking the product in the flotation tank as middling, returning to the foam flotation rougher flotation operation in the step (4), and performing flotation on the foam product to obtain a final concentrate product.
Through detection, the BaO content in the dry basis of the concentrate obtained in the embodiment is 52%, and the concentrate can be used as a raw material of barium chemical industry.
And combining the centrifugal tailings and the flotation tailings to be used as final tailings, and carrying out solution pH measurement and toxicity leaching analysis according to hazardous waste identification standard-leaching toxicity identification (GB 5085.3-2007). The detection result is as follows: the pH value of the final tailings is 7.5, and the concentration of barium and compounds thereof in the final tailings leaching solution is 25.6mg/L, so that the requirement of filling barium slag into a field for landfill is met.
Example 3
The barium slag used in this example was barium slag of Guizhou, barium carbonate 24%, barium sulfate 11%, BaS 3%, carbon 6%, and SiO2Content 22%, pH = 11.6.
In the slag storage water of the phosphorization plant used in the embodiment, the phosphate radical concentration is 5500mg/L, the sulfate radical concentration is 15000mg/L, and the pH value is = 1.9.
The acidified water glass used in this example was prepared with water glass and sulfuric acid in a mass ratio of 100: 4, and the modulus of the water glass was 2.8.
The method for harmlessly converting barium slag and recycling barium salt in the embodiment comprises the following specific steps:
(1) mixing barium slag and slag reservoir water of a phosphorization plant according to the mass ratio of 10: 5, performing wet grinding, and sieving, wherein the mass of minerals with the particle size of less than 0.15mm after grinding is equal to 98% of the total mass of raw ores, so as to obtain ore pulp;
(2) rinsing and centrifugally separating the ore pulp obtained in the step (1) by using an SL type centrifugal separator, wherein the separated mineral with high density is centrifugal concentrate, and the mineral with low density is centrifugal tailings; the concentration of the centrifugal separation feeding material is 10 percent, the rotating speed of a rotary drum of the centrifugal separator is 700rpm, the ore pulp treatment capacity is 1.2Kg/min, and the flow rate of the rinsing liquid is 0.5L/min;
(3) settling and concentrating the centrifugal concentrate obtained in the step (2) to obtain concentrated underflow and overflow liquid, and returning the overflow liquid to the step (2) to be used as rinsing liquid; the concentration of the settled underflow is 64%;
(4) wet grinding and sieving the concentrated underflow obtained in the step (3), wherein the mass of the ore with the granularity of less than 0.074mm after wet grinding is equal to 75 percent of the total raw ore mass; placing wet-milled ore pulp into a flotation tank, adding slag storage water of a phosphating plant for size mixing until the mass concentration of the ore pulp is 25%, the pH value of the ore pulp is 5.5, adding acidified water glass, performing flotation on raw ore with the dosage of 200g/t, stirring for 2min, adding sodium laurate with the dosage of 400g/t, performing flotation on the raw ore, stirring for 3min, finally adding alkylphenol ether phosphate with the dosage of 100g/t, performing flotation on the raw ore, stirring for 2min, performing inflation flotation for 5min, taking a product in the flotation tank as flotation tailings, and performing flotation on a foam product as rougher concentrate;
(5) and (3) placing the roughed concentrate obtained in the step (4) into a flotation tank, adding slag storage water of a phosphating plant for size mixing until the pH value is 5.5, adding acidified water glass, performing flotation on the raw ore with the use amount of 100g/t, stirring for 2min, performing air flotation for 3min, taking the product in the flotation tank as middling, returning to the foam flotation rougher flotation operation in the step (4), and performing flotation on the foam product to obtain a final concentrate product.
Through detection, the BaO content in the dry basis of the concentrate obtained in the embodiment is 58%, and the concentrate can be used as a raw material of barium chemical industry.
And combining the centrifugal tailings and the flotation tailings to be used as final tailings, and carrying out solution pH measurement and toxicity leaching analysis according to hazardous waste identification standard-leaching toxicity identification (GB 5085.3-2007). The detection result is as follows: the pH value of the final tailings is 7.5, and the concentration of barium and compounds thereof in the final tailings leaching solution is 16.5mg/L, so that the requirement of filling barium slag into a field for landfill is met.
Example 4
The barium residue used in this example was barium residue from Guizhou, which had a barium carbonate content of 21%, a barium sulfate content of 8%, a BaS content of 3.5%, carbon 5%, and SiO2Content 25%, pH = 11.6.
In the slag storage water of the phosphorization plant used in the embodiment, the phosphate radical concentration is 5500mg/L, the sulfate radical concentration is 15000mg/L, and the pH value is = 1.9.
The acidified water glass used in this example was prepared with water glass and sulfuric acid in a mass ratio of 100: 5, and the modulus of the water glass was 2.6.
The method for harmlessly converting barium slag and recycling barium salt in the embodiment comprises the following specific steps:
(1) mixing barium slag and slag reservoir water of a phosphorization plant according to the mass ratio of 10: 8, performing wet grinding, and sieving, wherein the mass of minerals with the particle size of less than 0.15mm after grinding is equal to 98% of the total mass of raw ores, so as to obtain ore pulp;
(2) rinsing and centrifugally separating the ore pulp obtained in the step (1) by using an SL type centrifugal separator, wherein the separated mineral with high density is centrifugal concentrate, and the mineral with low density is centrifugal tailings; the concentration of the centrifugal separation feeding material is 15%, the rotating speed of a rotary drum of the centrifugal separator is 800rpm, the ore pulp treatment capacity is 0.6Kg/min, and the flow rate of the rinsing liquid is 0.4L/min;
(3) settling and concentrating the centrifugal concentrate obtained in the step (2) to obtain concentrated underflow and overflow liquid, and returning the overflow liquid to the step (2) to be used as rinsing liquid; the concentration of the settled underflow is 64%;
(4) wet grinding and sieving the concentrated underflow obtained in the step (3), wherein the mass of ore with the granularity of less than 0.074mm after wet grinding is equal to 70% of the total raw ore mass; placing wet-milled ore pulp into a flotation tank, adding slag storage water of a phosphating plant for size mixing until the mass concentration of the ore pulp is 25 percent, the pH value of the ore pulp is 5.5, adding acidified water glass with the dosage of 500g/t for floating the raw ore, stirring for 2min, adding a mixed collecting agent (sodium palmitate: sodium laurate =2: 1) with the dosage of 200g/t for floating the raw ore, stirring for 3min, finally adding alkylphenol ether phosphate with the dosage of 150g/t for floating the raw ore, stirring for 1min, aerating for 5min, taking a product in the flotation tank as flotation tailings, and taking a flotation foam product as a rougher concentrate;
(5) and (3) placing the roughed concentrate obtained in the step (4) into a flotation tank, adding slag storage water of a phosphating plant for size mixing until the pH value is 5.5, adding acidified water glass, performing flotation on the raw ore with the use amount of 60g/t, stirring for 2min, performing air flotation for 3min, taking the product in the flotation tank as middling, returning to the foam flotation rougher flotation operation in the step (4), and performing flotation on the foam product to obtain a final concentrate product.
Through detection, the BaO content in the dry basis of the concentrate obtained in the embodiment is 50.5%, and the concentrate can be used as a raw material of barium chemical industry.
Combining the centrifugal tailings and the flotation tailings to be used as final tailings, and carrying out solution pH measurement and toxicity leaching analysis according to hazardous waste identification standard-leaching toxicity identification (GB 5085.3-2007). The detection result is as follows: the pH value of the final tailings is 7.5, and the concentration of barium and compounds thereof in the final tailings leaching solution is 18.9mg/L, so that the requirement of barium slag on filling in a landfill is met.
Claims (10)
1. A method for harmlessly transforming barium slag and recovering barium salt is characterized by comprising the following steps:
(1) harmless treatment of barium slag: mixing barium slag and slag reservoir water of a phosphorization plant, performing wet grinding, and sieving to obtain ore pulp;
(2) centrifugal separation: rinsing and centrifugally separating the ore pulp obtained in the step (1) by using a centrifugal separator, wherein the separated mineral with high density is centrifugal concentrate, and the mineral with low density is centrifugal tailings;
(3) concentration: settling and concentrating the centrifugal concentrate obtained in the step (2) to obtain concentrated underflow and overflow liquid, and returning the overflow liquid to the step (2) to be used as rinsing liquid;
(4) and (3) foam flotation roughing: wet grinding and sieving the concentrated underflow obtained in the step (3) to obtain wet grinding ore pulp; placing the wet-milled ore pulp into a flotation tank, adding slag storage water of a phosphorization factory for pulp mixing, adding an inhibitor, stirring, adding a collecting agent, stirring, finally adding a foaming agent, stirring, performing air flotation, taking a product in the flotation tank as flotation tailings, and taking a flotation foam product as roughing concentrate;
(5) foam flotation and fine selection: placing the roughed concentrate obtained in the step (4) into a flotation tank, adding slag storage water of a phosphating factory for size mixing, adding an inhibitor, stirring, performing aerated flotation, taking the product in the flotation tank as middlings, returning to the foam flotation rougher flotation operation in the step (4), and performing flotation on the foam product to obtain a final concentrate product;
in the barium slag, the barium carbonate content is 20-25 wt%, the barium sulfate content is 8-12 wt%, the BaS content is 2.5-4.5 wt%, the carbon is 5-8 wt%, and the SiO is2The content is 20-25 wt%; in the slag storage water of the phosphating plant, the concentration of phosphate radical is 4500-6000 mg/L, the concentration of sulfate radical is 12000-16000 mg/L, and the pH value is 1.8-2.2.
2. The method for detoxifying and recovering barium salt according to claim 1, wherein in the step (1), the barium slag is wet-milled by a rod mill, and the mass of the mineral with the granularity of less than 0.15mm after milling is equal to more than 90% of the total raw mineral mass; the mass of the water in the slag storage is 0.5-0.8 time of that of the barium slag.
3. The method for detoxifying and recovering barium salt as claimed in claim 1 or 2 wherein in step (2) the centrifugal concentrator is an SL type centrifugal concentrator; the concentration of the centrifugally separated feed is 10-20%, the rotating speed of a rotary drum of the centrifugal separator is 500-800 rpm, the pulp treatment amount is 0.6-1.5 Kg/min, and the flow rate of the rinsing liquid is 0.4-1.0L/min.
4. The method for detoxifying and recovering barium salt as claimed in any one of claims 1 to 3 wherein in step (3) said concentrated underflow has a concentration of 60 to 64%.
5. The method for detoxifying the barium slag and recovering the barium salt according to any one of claims 1 to 4, wherein in the step (4), the concentrated underflow is wet-milled by a rod mill, and the mass of the mineral with the particle size of less than 0.074mm after wet milling is 65-75% of the total raw mineral mass; adding water in a slag storage, and mixing until the mass concentration of the ore pulp is 25-38% and the pH value is 5.5-6.5.
6. The method for detoxifying the barium slag and recovering the barium salt as claimed in any one of claims 1 to 5, wherein in step (4) or step (5), the inhibitor is water glass acidified by sulfuric acid, the mass ratio of the water glass to the sulfuric acid is 100:1 to 5, and the modulus of the water glass is 2.5 to 3.0.
7. The method for detoxifying and recovering barium salt according to any one of claims 1 to 6, wherein in the step (4), the amount of the inhibitor is 200 to 500 g/t; and stirring for 2-4 min after adding the inhibitor.
8. The method for detoxifying the barium slag and recovering the barium salt according to any one of claims 1 to 7, wherein in the step (4), the collecting agent is one or more than two of sodium palmitate, sodium myristate and sodium laurate; the using amount of the collecting agent is 100-500 g/t; and stirring for 3-5 min after adding the collecting agent.
9. The method for detoxifying the barium slag and recovering the barium salt according to any one of claims 1 to 8, wherein in the step (4), the foaming agent is one or more of alkyl phosphate, ethoxylated fatty acid phosphate and alkylphenol ether phosphate; the amount of the foaming agent is 50-200 g/t; adding a foaming agent and stirring for 1-2 min; and the time of the air flotation is 2-8 min.
10. The method for detoxifying and recovering barium salt according to any one of claims 1 to 9, wherein in the step (5), the slurry is mixed until the pH value of the slurry is 5.5 to 6.5; the dosage of the inhibitor is 50-100 g/t, and the stirring time is 2-5 min after the inhibitor is added; and the time of the air flotation is 3-5 min.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4182785A (en) * | 1978-04-06 | 1980-01-08 | Anglo-American Clays Corporation | Process for improving rheology of clay slurries |
| RU2008139611A (en) * | 2006-03-07 | 2010-04-20 | Маратон Ойл Кэнада Корпорейшн (Ca) | PROCESSING ASPHALT-CONTAINING TAILS |
| CA2693879A1 (en) * | 2010-02-22 | 2011-08-22 | Titanium Corporation Inc. | A method for processing froth treatment tailings |
| CN103706488A (en) * | 2013-12-31 | 2014-04-09 | 中蓝连海设计研究院 | Reverse flotation technology of phosphate ore in alkaline medium |
| CN105236783A (en) * | 2015-10-10 | 2016-01-13 | 南风化工集团股份有限公司 | Barium sulfate waste residue comprehensive utilization method and wall filling material |
| CN109967229A (en) * | 2019-04-26 | 2019-07-05 | 广东省资源综合利用研究所 | A kind of method that weathering type haplotypite containing vanadium selects smelting recycling vanadium ferrotianium |
| WO2019210533A1 (en) * | 2018-05-02 | 2019-11-07 | 东北大学 | Harmless disposal method for cyanidation tailing |
| CN209872391U (en) * | 2019-05-20 | 2019-12-31 | 长沙中硅水泥技术开发有限公司 | System for utilize barium sediment preparation barium sulfate |
| CN111135957A (en) * | 2020-01-13 | 2020-05-12 | 中国科学院地球化学研究所 | Method for recovering carbon from barium slag through flotation |
| CN111644269A (en) * | 2020-06-02 | 2020-09-11 | 中蓝长化工程科技有限公司 | Method for comprehensively utilizing electrolytic manganese slag resources |
-
2020
- 2020-11-16 CN CN202011275778.5A patent/CN114505166B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4182785A (en) * | 1978-04-06 | 1980-01-08 | Anglo-American Clays Corporation | Process for improving rheology of clay slurries |
| RU2008139611A (en) * | 2006-03-07 | 2010-04-20 | Маратон Ойл Кэнада Корпорейшн (Ca) | PROCESSING ASPHALT-CONTAINING TAILS |
| CA2693879A1 (en) * | 2010-02-22 | 2011-08-22 | Titanium Corporation Inc. | A method for processing froth treatment tailings |
| CN103706488A (en) * | 2013-12-31 | 2014-04-09 | 中蓝连海设计研究院 | Reverse flotation technology of phosphate ore in alkaline medium |
| CN105236783A (en) * | 2015-10-10 | 2016-01-13 | 南风化工集团股份有限公司 | Barium sulfate waste residue comprehensive utilization method and wall filling material |
| WO2019210533A1 (en) * | 2018-05-02 | 2019-11-07 | 东北大学 | Harmless disposal method for cyanidation tailing |
| CN109967229A (en) * | 2019-04-26 | 2019-07-05 | 广东省资源综合利用研究所 | A kind of method that weathering type haplotypite containing vanadium selects smelting recycling vanadium ferrotianium |
| CN209872391U (en) * | 2019-05-20 | 2019-12-31 | 长沙中硅水泥技术开发有限公司 | System for utilize barium sediment preparation barium sulfate |
| CN111135957A (en) * | 2020-01-13 | 2020-05-12 | 中国科学院地球化学研究所 | Method for recovering carbon from barium slag through flotation |
| CN111644269A (en) * | 2020-06-02 | 2020-09-11 | 中蓝长化工程科技有限公司 | Method for comprehensively utilizing electrolytic manganese slag resources |
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