CN112474060A - Method for promoting heteropolar ore sulfuration flotation by using fluorine ions - Google Patents
Method for promoting heteropolar ore sulfuration flotation by using fluorine ions Download PDFInfo
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- CN112474060A CN112474060A CN202011280071.3A CN202011280071A CN112474060A CN 112474060 A CN112474060 A CN 112474060A CN 202011280071 A CN202011280071 A CN 202011280071A CN 112474060 A CN112474060 A CN 112474060A
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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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/002—Inorganic compounds
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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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
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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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
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Abstract
The invention discloses a method for promoting heteropolar ore sulfidation flotation by using fluoride ions, which is characterized in that a fluorinating agent is added in the heteropolar ore sulfidation flotation process, the fluoride ions are used for corroding the surface of the heteropolar ore, so that Si on the surface of the heteropolar ore is separated, and Zn covered by Si is exposed, thereby increasing the reactive active sites of the heteropolar ore and a sulfidizing agent, improving the capacity of adsorbing a collecting agent on the surface of the heteropolar ore, and finally improving the recovery rate of the heteropolar ore. The method can effectively solve the problem of low vulcanization efficiency of the hemimorphic ore caused by low Zn content of the mineral surface vulcanization reaction sites, and effectively improve the vulcanization flotation recovery efficiency of the hemimorphic ore.
Description
Technical Field
The invention belongs to the field of mineral flotation separation, relates to a method for flotation separation of hemimorphite, and particularly relates to a method for improving the vulcanization flotation effect of hemimorphite by modifying the surface of hemimorphite by using fluorine ions.
Background
Zinc is an important nonferrous metal, is mainly used for preparing zinc alloy and galvanizing in industry, and meanwhile, zinc is widely applied to the fields of biomedicine, catalysts, sensor elements and the like. At present, zinc mainly comes from zinc sulfide ores, but as the reserves of the zinc sulfide ores are less and less, the exploitation and utilization of zinc oxide ores are gradually paid attention.
The hemimorphite belongs to one of main minerals in the zinc oxide ore and is derived from an oxidation zone of sulfide minerals, so compared with the zinc sulfide ore, the hemimorphite is difficult to select due to the problems of high oxidation rate, large mud content, more inevitable ions in ore pulp and the like. At present, the flotation of the hemimorphite is mainly carried out by sulfide flotation, namely, the surface of the hemimorphite is vulcanized by using a vulcanizing agent, so that the surface of the hemimorphite has the property of sulfide minerals, wherein the most common methods are a sulfide-amine flotation method and a sulfide-xanthate flotation method. The sulfide-amine flotation method is the main method for flotation recovery of zinc oxide ore at present, but the method is easily influenced by slime, and if desliming treatment is carried out, a large amount of zinc metal is lost; the sulfurization-xanthate flotation method is not sensitive to slime, but has low sulfurization efficiency and needs to consume a large amount of metal ions, and the main reason of the low sulfurization rate of the method is that sulfurization reaction sites on the surface of the hemimorphite are easily covered by Si components, so that the Zn content is low. Therefore, to increase the sulfidation rate of the sulfidation-xanthate flotation process, Si on the surface of the hemimorphite needs to be destroyed to expose the sulfidation reaction sites.
It is known that fluoride ions have a certain corrosion action on the surface of silicate ores, so that the fluoride ions can be used for modifying the surface of the hemimorphic ores, the Si-O structure on the surface of the hemimorphic ores is damaged, Zn is exposed, the vulcanization reaction sites on the surface of the hemimorphic ores are increased, the vulcanization rate is improved, and the aim of improving the flotation recovery rate is fulfilled.
Disclosure of Invention
In order to solve the problems of low vulcanization efficiency and poor flotation effect of the hemimorphite caused by the fact that the surface vulcanization reaction sites are covered by the Si component, the invention provides a method for promoting the hemimorphite vulcanization flotation by utilizing fluorine ions.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for promoting heteropolar ore sulfidation flotation by using fluorine ions comprises the following steps:
1) grinding the hemimorphous ore raw ore to be treated or the mixed ore sample thereof, preparing the hemimorphous ore raw ore or the mixed ore sample thereof into ore pulp with the mass concentration of 25-35% with water, and then mixing the pulp for 2 min;
2) adding a fluorinating agent into the ore pulp obtained in the step 1), and mixing the pulp for 5 min;
3) adding a vulcanizing agent into the ore pulp obtained in the step 2), mixing for 5min, adding an activating agent, and mixing for 3 min;
4) and (3) carrying out flotation on the ore pulp obtained in the step 3) according to a conventional process to obtain the hemimorphic ore concentrate.
Step 1), the content of the hemimorphite in the hemimorphite raw ore is 5-20%; the mixed ore sample is prepared by mixing hemimorphite raw ore and gangue minerals such as quartz and the like according to the mass ratio of 1: 0.5-10. The ore grinding is to grind the raw ore to 80-90% of particles with the fineness of-0.074 mm, or to grind the mixed ore sample to the fineness of 150-325 meshes.
The fluorinating agent in the step 2) is HF or NaF, and the addition amount of the fluorinating agent is 5.0 multiplied by 10-5～10.0×10-5mol/L。
The vulcanizing agent in the step 3) is Na2S or NaHS, and the activator is CuSO4Or Pb (NO)3)2The addition amounts of both are the same and are 1.0X 10-3～5.0×10-3mol/L。
By utilizing the principle that fluoride ions can corrode silicate minerals, HF or NaF is added into heteropolar ore pulp, and the fluoride ions can be hydrolyzed into (HF) in the ore pulp2And HF2 -And the silicon-based carbon material is adsorbed on the Si component on the surface of the heteropolar ore, so that the electron cloud of the Si-O bond is deviated, the polarity of the bond is increased, the bond energy is weakened, and finally the bond is broken. Because of the fracture of Si-O, the Si component on the surface of the hemimorphite is separated, so that the Zn component originally shielded by Si is exposed, and the reaction sites of the hemimorphite and the vulcanizing agent are increased, thereby improving the vulcanization rate on the surface of the hemimorphite and finally improving the vulcanization activation flotation effect of the hemimorphite.
The invention has the following remarkable advantages:
1) the invention utilizes fluorine ions to carry out corrosion on the Si component on the surface of the hemimorphite, so that the surface vulcanization reaction site Zn of the hemimorphite is greatly increased, thereby improving the vulcanization rate of the hemimorphite and greatly solving the problem of poor flotation effect caused by low vulcanization rate of the hemimorphite vulcanization flotation.
2) The method has the advantages of simple process flow, simple medicament system and convenient operation, can obviously improve the recovery effect of the hemimorphite, and has good industrial feasibility.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Respectively crushing and screening the hemimorphic ore pure mineral sample and the quartz pure mineral sample into 150-mesh powder with the particle size of 325 meshes, mixing the hemimorphic ore pure mineral sample and the quartz pure mineral sample according to the mass ratio of 1:2.5, putting 100g of the hemimorphic ore pure mineral sample into a flotation tank, adding water to prepare ore pulp with the mass concentration of 30%, and carrying out size mixing for 2min by adopting an XFGII type suspension tank flotation machine under the condition of the rotating speed of 1992 r/min. After the size mixing is finished, adding a proper amount of 10 multiplied by 10-4mol/L NaF solution (NaF is added in an amount of 10X 10)-5mol/L) for pretreatment and size mixing for 5 min; after the pretreatment of the ore pulp is finished, the pulp is pretreated by 6.0 x 10-4Adding vulcanizing agent Na in sequence according to the adding amount of mol/L2S and the activator Pb (NO)3)2Respectively pulping for 5min and 3min, sequentially adding collecting agent isoamyl xanthate and foaming agent methyl isobutyl carbinol according to the addition amounts of 12.5mg/L and 10mg/L, respectively pulping for 2min and 1min, and finally floating for 3 min. And after the flotation is finished, drying and weighing the obtained concentrate (foam product) and tailings (in-tank product) respectively, and calculating the recovery rate of the concentrate (foam product) and tailings, wherein the zinc grade of the obtained concentrate is 40.51%, and the recovery rate of the hemimorphite is 85.30%.
Example 2
Respectively crushing and screening the heteropolar ore pure mineral sample and the quartz pure mineral sample into 150-mesh and 325-mesh materials, mixing the heteropolar ore pure mineral sample and the quartz pure mineral sample according to the mass ratio of 1:6, putting 100g of the heteropolar ore pure mineral sample and the quartz pure mineral sample into a flotation tank, adding water to prepare ore pulp with the mass concentration of 25%, and adopting an XFGII type hanging tank flotation machine at the rotating speed of 1992 r/minAnd (5) mixing the slurry for 2min under the condition. After the size mixing is finished, adding a proper amount of 10 multiplied by 10-4mol/L HF solution (make the addition of HF 5X 10)-5mol/L) for pretreatment and size mixing for 5 min; after the pretreatment of the ore pulp is finished, the pulp is pretreated by 5.0 multiplied by 10-4Adding a vulcanizing agent NaHS and an activator Pb (NO) in sequence according to the addition amount of mol/L3)2Respectively pulping for 2min and 1min, sequentially adding collecting agent isoamyl xanthate and foaming agent methyl isobutyl carbinol according to the addition amounts of 12.5mg/L and 10mg/L, respectively pulping for 2min and 1min, and finally floating for 3 min. After the flotation is finished, the obtained concentrate (foam product) and tailings (product in the tank) are respectively dried and weighed, and the recovery rate is calculated, so that the zinc grade of the obtained concentrate is 39.53 percent, and the recovery rate of the hemimorphite is 84.70 percent.
Example 3
Respectively crushing and screening the hemimorphic ore pure mineral sample and the quartz pure mineral sample into 150-mesh 325-mesh powder, mixing the hemimorphic ore pure mineral sample and the quartz pure mineral sample according to the mass ratio of 1:1, placing 100g of the hemimorphic ore pure mineral sample into a flotation tank, adding water to prepare ore pulp with the mass concentration of 35%, and carrying out size mixing for 2min by adopting an XFGII type suspension tank flotation machine under the condition that the rotating speed is 1992 r/min. After the size mixing is finished, adding a proper amount of 10 multiplied by 10-4mol/L NaF solution (NaF added in 5X 10)-5mol/L) for pretreatment and size mixing for 5 min; after the pretreatment of the ore pulp is finished, the pretreatment is carried out according to the proportion of 7.0 multiplied by 10-4Adding a vulcanizing agent NaHS and an activating agent CuSO into the mixture in sequence according to the mol/L addition amount4Respectively pulping for 5min and 3min, sequentially adding collecting agent isoamyl xanthate and foaming agent methyl isobutyl carbinol according to the addition amounts of 12.5mg/L and 10mg/L, respectively pulping for 2min and 1min, and finally floating for 3 min. After the flotation is finished, the obtained concentrate (foam product) and tailings (product in the tank) are respectively dried and weighed, and the recovery rate is calculated, so that the zinc grade of the obtained concentrate is 41.40%, and the recovery rate of the hemimorphite is 83.10%.
Example 4
The hemimorphic ore raw ore is from a Yunan Landai mining area, wherein the zinc content is 11.8 percent, the hemimorphic ore content is 5.1 percent, the raw ore is crushed and ground until the particle size is 85 percent of-0.074 mm, 500g of the hemimorphic ore raw ore is placed in a flotation tank, water is added to prepare ore pulp with the mass concentration of 30 percent, and the pulp is mixed for 2 min; after the size mixing is finished, addingProper concentration is 10 multiplied by 10-4mol/L NaF solution (NaF added in 8X 10)- 5mol/L) for pretreatment and size mixing for 5 min; after the pretreatment of the ore pulp is finished, the pretreatment is carried out according to the proportion of 8.0 multiplied by 10-4Adding vulcanizing agent Na in sequence according to the adding amount of mol/L2S and an activator CuSO4Respectively pulping for 5min and 3min, sequentially adding collecting agent isoamyl xanthate and foaming agent methyl isobutyl carbinol according to the addition amounts of 12.5mg/L and 10mg/L, respectively pulping for 2min and 1min, and finally floating for 3 min. And after the flotation is finished, drying and weighing the obtained concentrate (foam product) and tailings (in-tank product) respectively, and calculating the recovery rate of the concentrate and the tailings, wherein the recovery rate of the hemimorphite is 83.1 percent, and the grade of zinc in the concentrate is 34.2 percent.
Example 5
The hemimorphic ore raw ore is from a certain mining area in Hunan, wherein the zinc content is 15.1 percent, the hemimorphic ore content is 7.6 percent, the raw ore is crushed and ground until the particle size is 85 percent of-0.074 mm, 500g of the hemimorphic ore raw ore is placed in a flotation tank, water is added to prepare ore pulp with the mass concentration of 35 percent, and the pulp is mixed for 2 min; after the size mixing is finished, adding a proper amount of 10 multiplied by 10-4mol/L HF solution (make the addition of HF 10X 10)- 5mol/L) for pretreatment and size mixing for 5 min; after the pretreatment of the ore pulp is finished, the pulp is pretreated by 10.0 x 10-4Adding a vulcanizing agent NaHS and an activator Pb (NO) in sequence according to the addition amount of mol/L3)2Respectively pulping for 5min and 3min, sequentially adding collecting agent isoamyl xanthate and foaming agent methyl isobutyl carbinol according to the addition amounts of 12.5mg/L and 10mg/L, respectively pulping for 2min and 1min, and finally floating for 3 min. And after the flotation is finished, drying and weighing the obtained concentrate (foam product) and tailings (in-tank product) respectively, and calculating the recovery rate of the concentrate and the tailings, wherein the recovery rate of the hemimorphite is 85.1 percent, and the grade of zinc in the concentrate is 34.7 percent.
Comparative example 1
The hemimorphic ore pure mineral sample and the quartz pure mineral sample which are in the same batch as in the embodiment 2 are respectively crushed and sieved into 150-mesh 325 meshes, then the hemimorphic ore pure mineral sample and the quartz pure mineral sample are mixed according to the mass ratio of 1:6, 100g of the hemimorphic ore pure mineral sample and the quartz pure mineral sample are placed in a flotation tank, water is added to prepare ore pulp with the mass concentration of 25 percent, and the ore pulp is mixed for 2min by adopting an XFGII type suspension tank flotation machine under the condition that the rotating speed is 1992 r/min. After the size mixing is finishedWithout addition of fluorinating agent, the amount of the fluorine-containing compound is 5.0X 10-4Adding a vulcanizing agent NaHS and an activator Pb (NO) in sequence according to the addition amount of mol/L3)2Respectively pulping for 2min and 1min, sequentially adding collecting agent isoamyl xanthate and foaming agent methyl isobutyl carbinol according to the addition amounts of 12.5mg/L and 10mg/L, respectively pulping for 2min and 1min, and finally floating for 3 min. After the flotation is finished, the obtained concentrate (foam product) and tailings (product in the tank) are respectively dried and weighed, and the recovery rate is calculated, so that the zinc grade of the obtained concentrate is 34.2 percent, and the recovery rate of the hemimorphite is 74.3 percent.
Comparative example 2
Crushing and grinding the same batch of raw ores (the zinc content is 11.8 percent and the hemimorphic ore content is 5.1 percent) from the Yunan Lanping area as example 4 to 85 percent of-0.074 mm, putting 500g of the raw ores into a flotation tank, adding water to prepare ore pulp with the mass concentration of 35 percent, and carrying out size mixing for 2 min; after the size mixing is finished, respectively, the fluorinating agent is not added, but the slurry is directly mixed according to the proportion of 8.0 multiplied by 10-4Adding vulcanizing agent Na in sequence according to the adding amount of mol/L2S and an activator CuSO4Respectively pulping for 5min and 3min, sequentially adding collecting agent isoamyl xanthate and foaming agent methyl isobutyl carbinol according to the addition amounts of 12.5mg/L and 10mg/L, respectively pulping for 2min and 1min, and finally floating for 3 min. And after the flotation is finished, drying and weighing the obtained concentrate (foam product) and tailings (product in the tank) respectively, and calculating the recovery rate of the concentrate and the tailings. No fluorinating agent is added in the separation process, the recovery rate of the obtained hemimorphite is 68.2 percent, and the grade of the zinc in the concentrate is 34.6 percent.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. A method for promoting heteropolar ore sulfuration flotation by using fluorine ions is characterized by comprising the following steps: the method comprises the following steps:
1) grinding the hemimorphous ore raw ore to be treated or the mixed ore sample thereof, preparing the hemimorphous ore raw ore or the mixed ore sample thereof into ore pulp with the mass concentration of 25-35% with water, and then mixing the pulp for 2 min;
2) adding a fluorinating agent into the ore pulp obtained in the step 1), and mixing the pulp for 5 min;
3) adding a vulcanizing agent into the ore pulp obtained in the step 2), mixing for 5min, adding an activating agent, and mixing for 3 min;
4) and (3) carrying out flotation on the ore pulp obtained in the step 3) according to a conventional process to obtain the hemimorphic ore concentrate.
2. The method for promoting hemimorphite sulfidation flotation using fluorine ion according to claim 1, characterized in that: step 1), the content of the hemimorphite in the hemimorphite raw ore is 5-20%; the mixed ore sample is prepared by mixing hemimorphite raw ore and gangue minerals according to the mass ratio of 1: 0.5-10.
3. The method for promoting hemimorphite sulfidation flotation using fluorine ion according to claim 1, characterized in that: in the step 1), the ore grinding is to grind the raw ore to 80-90% of particles with the fineness of-0.074 mm, or grind the mixed ore sample to the fineness of 150-325 meshes.
4. The method for promoting hemimorphite sulfidation flotation using fluorine ion according to claim 1, characterized in that: the fluorinating agent in the step 2) is HF or NaF, and the addition amount of the fluorinating agent is 5.0 multiplied by 10-5～10.0×10-5mol/L。
5. The method for promoting hemimorphite sulfidation flotation using fluorine ion according to claim 1, characterized in that: the vulcanizing agent in the step 3) is Na2S or NaHS, and the activator is CuSO4Or Pb (NO)3)2The addition amounts of both are the same and are 1.0X 10-3～5.0×10-3mol/L。
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2020
- 2020-11-16 CN CN202011280071.3A patent/CN112474060A/en active Pending
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| WO2002059386A1 (en) * | 2001-01-24 | 2002-08-01 | Companhia Mineira De Metais | Improved beneficiation process for concentration/calcination of zinc silicate ores and minerals |
| CN102284372A (en) * | 2011-07-26 | 2011-12-21 | 昆明理工大学 | Flotation method for carbonate minerals |
| CN102489412A (en) * | 2011-12-26 | 2012-06-13 | 昆明理工大学 | Method for activating calamine in flotation process |
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