CN112844855A - Flotation reagent for selectively separating galena and sphalerite and application method thereof - Google Patents
Flotation reagent for selectively separating galena and sphalerite and application method thereof Download PDFInfo
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- CN112844855A CN112844855A CN202110009287.4A CN202110009287A CN112844855A CN 112844855 A CN112844855 A CN 112844855A CN 202110009287 A CN202110009287 A CN 202110009287A CN 112844855 A CN112844855 A CN 112844855A
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- flotation
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- 238000005188 flotation Methods 0.000 title claims abstract description 152
- 229910052949 galena Inorganic materials 0.000 title claims abstract description 99
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052950 sphalerite Inorganic materials 0.000 title claims abstract description 82
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 49
- 239000003814 drug Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims description 77
- 239000012141 concentrate Substances 0.000 claims description 45
- 239000008396 flotation agent Substances 0.000 claims description 20
- 239000004088 foaming agent Substances 0.000 claims description 16
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 239000005083 Zinc sulfide Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical group [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000005215 alkyl ethers Chemical class 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 57
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 30
- 239000011707 mineral Substances 0.000 abstract description 30
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 238000011160 research Methods 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 19
- 238000000227 grinding Methods 0.000 description 12
- 238000009837 dry grinding Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 7
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000007790 scraping Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052981 lead sulfide Inorganic materials 0.000 description 2
- 229940056932 lead sulfide Drugs 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009291 froth flotation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PHLSTZGDRQZNJF-UHFFFAOYSA-M sodium;butan-2-yloxy-butan-2-ylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Na+].CCC(C)OP([O-])(=S)SC(C)CC PHLSTZGDRQZNJF-UHFFFAOYSA-M 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- 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
- B03D2201/04—Frothers
-
- 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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the field of mineral flotation, and particularly relates to a flotation reagent for selectively separating galena and sphalerite and an application method thereof
And agent B
Description
Technical Field
The invention belongs to the field of mineral flotation, and particularly relates to a selective flotation separation technology for mixed ores of lead sulfide and sphalerite.
Background
Lead resource ores in China are rich, but the types of the ores are complex, and the ores are often associated with various minerals, so that the lead resource ores have the characteristics of more lean ores and less rich ores. Galena is an important source of lead, sphalerite is a common associated mineral of the galena, and because the surface properties are similar, the galena and the sphalerite are difficult to separate by flotation, and flotation indexes are influenced. Therefore, the method has important significance for improving the selectivity and efficiency of the lead-zinc sulfide ore flotation reagent.
The most efficient and most common way to utilize the current stage of lead-zinc sulfide ore separation is by flotation. Flotation reagents are important components of flotation, and the development of novel flotation reagents is the most direct means for solving the problems in the field of mineral processing. The white drug is a common collector for lead-zinc sulfide ores, and has already been well applied in industry. According to the invention CN101254484A, the white drug has strong collecting capacity on sulfide ores, but has insufficient selectivity. The patent aims at the defect of white drug and increases the selective collecting capacity of the white drug by improving the structure of the white drug.
Disclosure of Invention
The invention aims to provide a flotation reagent capable of separating galena and sphalerite in a high-selectivity flotation mode.
The second object of the present invention is to provide a flotation separation method capable of separating galena and sphalerite with high selectivity.
The galena and the sphalerite are important minerals, but the galena and the sphalerite are similar in properties and are associated frequently, the flotation separation selectivity and the recovery rate of target minerals are not ideal, and aiming at the technical problem, the invention provides the following technical scheme:
a flotation reagent for selectively separating galena and blende, comprising a reagent a and a reagent B;
the medicament A is at least one of compounds with the structural formula 1;
formula 1
The medicament B is at least one of compounds with the structural formula of formula 2;
formula 2
R1Is H, C1～C3Alkyl of (C)5～C15Saturated cycloalkyl, phenyl, benzyl or acyl;
y is R2-O-or
Said R2Is C1～C6Alkyl, phenyl or benzyl of (a); said R3Is H or C1～C6Alkyl groups of (a); r4Is H, amino, C1～C6Alkyl of (a) or-N-R; r is C1～C3Alkyl groups of (a); and in formula 1, the atomic percentage of the N heteroatom is greater than or equal to 15%;
R5is C1～C15Alkyl of (C)5～C15Saturated cycloalkyl, phenyl or benzyl of (a);
and M is an alkali metal element or ammonium ion.
The research of the invention finds that the compound with the structure shown in the formula 1 is beneficial to realizing intramolecular synergy, and the effect of selectively distinguishing galena and sphalerite is achieved. In addition, the compound is combined with the compound shown in the formula 2, the intermolecular cooperation can be further realized, the further selective collection of galena can be facilitated, the zinc blende can be inhibited, the selective separation of the galena and the zinc blende can be realized, and the recovery rate and the grade of the galena can be improved.
The research of the invention discovers that the molecular structure of the first-level N-N-CS-O (N) in the molecule of the formula 1 and the cooperative control of active hydrogen are the key points for realizing intramolecular cooperation, improving the selective separation of galena and sphalerite and improving the recovery rate and grade of the galena. It has also been found that R can be further controlled1And Y is beneficial to further improving the separation selectivity of galena and sphalerite.
R1Is H, C1～C3Alkyl of (C)2～C4Acyl group of (4); further preferably H or acetyl;
preferably, R is2Is C1～C3Alkyl groups of (a);
preferably, R3Is H or C1～C3Alkyl groups of (a); r4Is H, amino or C1～C3Alkyl group of (1).
The present inventors have also found that the atomic percentage of the N heteroatom in the compound of formula 1 contributes to unexpectedly further improving the selectivity of separation of galena and sphalerite, and to further improving the synergy with formula 2.
Preferably, in the formula 1, the atomic percentage of the N heteroatom is 15-55 atm%; further preferably 25-55 atm%; more preferably 30 to 55 atm%.
Preferably, the medicament A is a mixture of two or more of the following compounds shown as formulas 1-A to 1-D;
further preferably, the medicament A is a mixture of a formula 1-C and a formula 1-D; the ratio of the two is 1-2: 1-2; more preferably 1-2: 1.
The research of the invention also finds that the adoption of the optimized compound reagent is beneficial to further improving the separation selectivity of galena and sphalerite and further improving the recovery rate and grade of the galena.
In the invention, besides the intramolecular synergy brought by the control of the molecular structure of the formula 1, the compound of the formula 1 and the compound of the formula 2 have unexpected intermolecular synergy, and the separation selectivity of galena and sphalerite can be further synergistically improved.
In the compound of formula 2 of the invention, R is5It may be a straight or branched chain alkyl group, or a phenyl group.
Preferably, R5Is C2～C6Alkyl group of (1).
Preferably, M is Na or K.
In the invention, the dosage of the medicament A and the medicament B is controlled, which is beneficial to further improving the intramolecular and intermolecular cooperativity of the medicament A and the medicament B in the aspect of realizing the selective separation of galena and sphalerite.
Preferably, the medicament A is 5 to 50 parts by weight, and more preferably 10 to 30 parts by weight; more preferably 10 to 15 parts;
45-90 parts of medicament B; preferably 65-80 parts; more preferably 80 to 85 parts.
In the present invention, a foaming agent is optionally added to the flotation agent in order to further improve the flotation separation efficiency and separation effect.
In the present invention, the foaming agent may be any material having a foaming function.
Preferably, the foaming agent is one of 2# oil, 4# oil, polyethylene glycol dibenzyl ether (glycerol benzyl oil), polypropylene glycol alkyl ether or W-02 foaming agent;
further preferably, the foaming agent is not more than 10 parts by weight; preferably 3 to 5 parts.
The invention also provides a selective flotation separation method of galena and sphalerite, which is characterized in that the flotation agent for the mixed ore containing the galena and the sphalerite is subjected to flotation to obtain concentrate enriched with the galena and tailings enriched with the sphalerite.
The research of the invention finds that the flotation reagent can improve the separation selectivity of galena and sphalerite unexpectedly and improve the recovery rate and grade of the galena due to the intramolecular and intermolecular cooperativity of the flotation reagent.
The flotation of the invention can be realized based on the existing means and equipment.
For example, the mixed ore can be crushed, ground and pulped by the existing means to obtain ore pulp, and then the flotation agent can be used for froth flotation based on the existing means and equipment to obtain the galena concentrate and the sphalerite tailings.
In the present invention, the mixed ore can be any mixed ore containing galena and sphalerite, for example, it contains galena and sphalerite, and it is also allowed to contain other useful ore or gangue mineral.
Preferably, the mixed ore is lead-zinc sulfide ore.
In the invention, the pH value of the ore pulp in the flotation process is 3-12; preferably 5 to 11; more preferably 8 to 10. In the technical scheme of the invention, due to the use of the medicament, the selective separation of galena and sphalerite can be effectively realized under the condition of high acid or high alkali.
In the invention, the dosage of the flotation reagent can be adjusted based on flotation requirements, and preferably, the dosage of the flotation reagent is 40-50 g/t; further preferably 45 to 50 g/t.
In the present invention, the flotation agent may be mixed in advance and then used for flotation. For example, formula 1 and formula 2 are mixed uniformly and then added to water together with a foaming agent to prepare a solution of a corresponding concentration, which is then used for flotation.
Advantageous effects
1. The invention discovers for the first time that the compound with the special structure shown in the formula 1 has intramolecular synergistic effect and can improve the selective separation of galena and sphalerite.
2. The compound of formula 1 and the compound of formula 2 are used together, and have intermolecular synergistic effect, so that the selective separation of galena and sphalerite can be further improved.
3. The technical scheme of the invention can effectively improve the selective separation of galena and sphalerite by virtue of the intramolecular and intermolecular synergy of the medicament, and can still show excellent selectivity even under the condition of high acid or high alkali which is difficult to separate in the prior art.
Drawings
FIG. 1 is a flotation scheme of the present invention
Detailed Description
The comparison effect of the invention and the prior art is illustrated by taking two single minerals of lead ore and sphalerite and a galena-sphalerite mixed mineral as examples.
The experimental procedure and dosage regimen for each of the examples are shown in FIG. 1.
TABLE 1 original taste and origin of minerals
Example 1
In order to verify the separation effect of the compound of formula 1 in the agent a of the present invention in each component when used alone, the galena and sphalerite in south of Hunan were used (the original grades are shown in table 1), the process shown in fig. 1 was used, the experiment was divided into two groups, the compound of formula 1 in this case was used alone as a flotation agent to perform flotation on the galena and sphalerite, the flotation parameters in each group of cases were the same, and the difference was only in the type of minerals, thereby comparing the flotation and separation effects of the compound of formula 1 in this case.
The flotation reagent of the present case: 95 parts of a compound of formula 1 (shown in table 2) and 5 parts of 2# oil.
The specific operation is as follows: 500g of concentrate ore (galena or sphalerite; the grain diameter is 3-0.5 mm) is dry-ground for 15min (the grain diameter after grinding is 0.0374-0.074 mm, a horizontal ball mill is adopted for dry-grinding, the grinding concentration is 35-40%), 2g of the grinded galena or sphalerite is weighed in each group and poured into a 40mL flotation tank, 40mL of deionized water is added, then the flotation reagent in the embodiment is added, the stirring is carried out for 3min to start the flotation, the flotation time is 3min, the concentrate is scraped to a concentrate basin along with the foam, and tailings are remained in the flotation tank. And (4) filtering and drying the concentrate and the tailings, weighing the concentrate and the tailings respectively, detecting the grade of the concentrate and calculating the recovery rate.
Table 2 shows the recovery rates of galena and sphalerite under different collectors of the compound of formula 1 (in this case, the concentration of the flotation agent is 45g/t, and the pH of the pulp is 9)
TABLE 2
Table 2 shows that the recovery rate of the lead ore after the flotation of the structure with relatively poor effect reaches 77.56% and the recovery rate of the sphalerite reaches 19.31% when the agent A is used alone, which shows that the separation effect of the agent A on lead and zinc sulfide ore is obvious. And as the percentage of N heteroatoms increases, the separation efficiency increases.
Example 2
In order to verify the separation effect of the compound of formula 1 in the agent A in each component when used in combination, the galena and the sphalerite in Hunan are adopted (the original grades are shown in table 1), the process shown in figure 1 is adopted, the experiment is divided into two groups, the compound of formula 1 in the case is used as a flotation agent to carry out flotation on the galena and the sphalerite, the flotation parameters of the cases in each group are the same, and the difference is only that the types of minerals are different, so that the flotation and separation effects of the compound of formula 1 in the case and the combined collecting agent in the case are compared
The flotation reagent of the present case: the total amount of the compound of the formula 1 is 95 parts, and the amount of the 2# oil is 5 parts.
The specific operation is as follows: dry grinding ore concentrates (galena or sphalerite, the particle size is 3-0.5 mm) for 15min (the particle size after grinding is 0.0374-0.074 mm, dry grinding is carried out by adopting a horizontal ball mill, the grinding concentration is 35-40%), weighing 2g of the grinded galena or sphalerite in each group, pouring into a 40mL flotation tank, adding 40mL of deionized water, adding the flotation reagent in the embodiment, stirring for 3min to start flotation, carrying out flotation for 3min, scraping the concentrate into a concentrate basin along with foam, and leaving tailings in the flotation tank. And (4) filtering and drying the concentrate and the tailings, weighing the concentrate and the tailings respectively, detecting the grade of the concentrate and calculating the recovery rate.
Table 3 shows the recovery rates of galena and sphalerite under the combined collectors of different compounds of formula 1 (in this case, the concentration of the flotation agent is 45g/t, and the pH of the pulp is 9).
TABLE 3
Table 3 shows that the recovery of lead ore is increased and the recovery of sphalerite is decreased after the compound of formula 1 is combined, and that the combination of the compound of formula 1 can increase the separation efficiency of the flotation reagent through a synergistic effect. Among them, the most effective is represented by the formula 1-C + formula 1-D (mass ratio: 1).
Example 3
In order to verify the influence of the compound of formula 2 in the combined chemical agent B on the recovery rate in the flotation, the method adopts galena and sphalerite in south of Hunan province (the original grades are shown in table 1), adopts the flow shown in fig. 1, and divides the experiment into two groups, wherein one of the compound of formula 2 and the compound of formula 1 (specifically, 1-C +1-D (mass ratio of 1: 1)) in the case are combined to serve as the flotation agent to perform flotation on the galena and the sphalerite, and the flotation parameters of the groups of cases are the same, and the difference is only that the types of minerals are different, so that the influence of the compound of formula 2 in the combined chemical agent B on the recovery rate in the flotation is compared.
The flotation reagent of the present case: 10 parts of the compound shown in the formula 1, 85 parts of the compound shown in the formula 2 and 5 parts of 2# oil.
The specific operation is as follows: dry grinding ore concentrate (the particle size is 3-0.5 mm) for 15min (the particle size is 0.0374-0.074 mm after grinding, dry grinding is carried out by adopting a horizontal ball mill, the grinding concentration is 35% -40%), weighing 2g of ground galena or zinc blende in each group, pouring into a 40mL flotation tank, adding 40mL of deionized water, adding the medicament in the case, stirring for 3min, starting flotation, wherein the flotation time is 3min, the concentrate is scraped to a concentrate basin along with foam, and tailings are remained in the flotation tank. And (4) filtering and drying the concentrate and the tailings, weighing the concentrate and the tailings respectively, detecting the grade of the concentrate and calculating the recovery rate.
Table 4 shows the recovery rates of galena and sphalerite under the combined collectors of different compounds of formula 2 (in this case, the concentration of the flotation agent is 45g/t, and the pH of the pulp is 9).
Table 4:
table 4 shows that the addition of the agent B can greatly improve the recovery rate of galena and reduce the recovery rate of sphalerite, and the synergistic effect of the agents can be further reflected. The best of these was sodium ethylxanthate, at which point the galena recovery was 96.67% and the sphalerite recovery was 4.98%, with almost complete separation of the two minerals.
Example 4
In the present example, in order to investigate the influence of the dosage ratio of the compound of formula 1 in the agent a to the compound of formula 2 in the agent B on the recovery rate in the flotation, the galena and the sphalerite in the south of the lake are adopted, the process shown in fig. 1 is adopted, the experiment is divided into two groups, one of the compounds of formula 2 in the present example (specifically, sodium ethylxanthate) and the compound of formula 1 (specifically, 1-C + formula 1-D (mass ratio of 1: 1)) are combined to be used as the flotation agent to float the galena and the sphalerite, the flotation parameters of each group are the same, and the difference is only that the types of minerals are different, so that the influence of the dosage ratio of the compound of formula 1 to the compound of formula 2 on the recovery rate in.
The flotation reagent of the present case: 95 parts of compound shown in formula 1 and compound shown in formula 2, and 5 parts of 2# oil.
The specific operation is as follows: dry grinding ore concentrates (galena or sphalerite, the particle size is 3-0.5 mm) for 15min (the particle size after grinding is 0.0374-0.074 mm, dry grinding is carried out by adopting a horizontal ball mill, the grinding concentration is 35-40%), weighing 2g of the grinded galena or sphalerite in each group, pouring into a 40mL flotation tank, adding 40mL of deionized water, adding the flotation reagent in the embodiment, stirring for 3min to start flotation, carrying out flotation for 3min, scraping the concentrate into a concentrate basin along with foam, and leaving tailings in the flotation tank. And (4) filtering and drying the concentrate and the tailings, weighing the concentrate and the tailings respectively, detecting the grade of the concentrate and calculating the recovery rate.
Table 5 shows the recovery rates of galena and sphalerite at different ratios of the amounts of the compounds of formula 1 and 2 (in this case, the concentration of the flotation agent is 45g/t, and the pH of the slurry is 9).
TABLE 5
Table 5 shows that a change in the ratio of agent a to agent B can affect the recovery of galena to zincblende when the ratio is maintained at 10: 85-15: the effect is the best among 80, the recovery rate of the galena is more than 95 percent, and the recovery rate of the sphalerite is only about 5 percent.
Example 5
Pulp pH is one of the most important parameters of the flotation process. This example explores the effect of pulp pH on the separation of galena and sphalerite from the flotation reagent of the present invention. The method adopts galena and sphalerite in Hunan, adopts the flow shown in figure 1, and the experiment is divided into two groups, wherein one compound (specifically sodium ethyl xanthate) in the formula 2 and a compound (specifically 1-C + formula 1-D (mass ratio of 1: 1)) in the formula 1 are combined to be used as a flotation agent to perform flotation on the galena and the sphalerite, and the flotation parameters of the groups are the same, but the difference is that the types of minerals are different.
The flotation reagent of the present case: 95 parts of the compound shown in the formula 1 and the compound shown in the formula 2 in total, in a ratio of 10: 85, 5 parts of No. 2 oil.
The specific operation is as follows: dry grinding ore concentrates (galena or sphalerite; the grain diameter is 3-0.5 mm) for 15min (the grain diameter after grinding is 0.0374-0.074 mm, dry grinding is carried out by adopting a horizontal ball mill, the grinding concentration is 35-40%), weighing 2g of the grinded galena or sphalerite in each group, pouring into a 40mL flotation tank, adding 40mL of deionized water, adding the flotation reagent in the embodiment, stirring for 3min to start flotation, scraping the concentrate into a concentrate basin along with foam for 3min, and leaving tailings in the flotation tank. And (4) filtering and drying the concentrate and the tailings, weighing the concentrate and the tailings respectively, detecting the grade of the concentrate and calculating the recovery rate.
Table 6 shows the recovery rates of galena and sphalerite at different pH values (concentration of flotation agent in this case 45 g/t).
TABLE 6
Table 6 shows that although the recovery of galena and zincblende is large in pH, the galena recovery rate is maintained at 85% or more and the zincblende recovery rate is maintained at 20% or less even under strong acid and strong alkali conditions; under the condition of weak alkali (pH 8-10), the recovery rate of galena is kept above 95%, and the recovery rate of sphalerite is kept about 5%. The flotation reagent has excellent selectivity on lead-zinc sulfide ore.
Example 6
This example explores the effect of flotation reagent concentration of the present invention on separation of galena and sphalerite. The method adopts galena and sphalerite in Hunan, adopts the flow shown in figure 1, the experiment is divided into two groups, one of the compounds in the formula 2 (specifically sodium ethyl xanthate) and the compound in the formula 1 (specifically 1-C +1-D (mass ratio of 1: 1)) in the case are combined to be used as flotation agents to carry out flotation on the galena and the sphalerite, the flotation parameters of each group are the same, and the difference is only that the types of minerals are different
The flotation reagent of the present case: 95 parts of the compound shown in the formula 1 and the compound shown in the formula 2 in total, in a ratio of 10: 85, 5 parts of No. 2 oil.
The specific operation is as follows: the method comprises the steps of dry grinding ore concentrates (the particle size is 3-0.5 mm) for 15min (the particle size is 0.0374-0.074 mm after grinding, the dry grinding is carried out by adopting a horizontal ball mill, the grinding concentration is 35-40%), weighing 2g of ground galena or zinc blende in each group, pouring into a 40mL flotation tank, adding 40mL of deionized water, adding the flotation reagent in the embodiment, stirring for 3min, starting flotation, wherein the flotation time is 3min, the ore concentrates are scraped to an ore concentrate basin along with foams, and tailings are remained in the flotation tank. And (4) filtering and drying the concentrate and the tailings, weighing the concentrate and the tailings respectively, detecting the grade of the concentrate and calculating the recovery rate.
Table 7 shows the recovery rates of galena and sphalerite at different concentrations of flotation reagent (pH 9 in the flotation pulp in this case).
TABLE 7
Table 7 shows that the change of the reagent has a large influence on the separation of galena and sphalerite, and the large or small dosage of the reagent is not beneficial to mineral separation, and the most suitable dosage of the reagent is 40-50 g/t, wherein the separation efficiency is most obvious at 45 g/t.
Example 7
To further demonstrate the selectivity of the flotation reagent in the present invention, flotation tests were performed on galena and sphalerite artificially mixed minerals (galena sphalerite ratio 1: 1, mixed minerals as in table 1). 95 parts of flotation reagent collecting agent, wherein the proportion of the formula 1 to the formula 2 is 10: 85, selecting a combined formula 1-C + formula 1-D (the mass ratio is 1: 1) in the formula 1; 5 parts of a foaming agent; concentration of flotation reagent: 45 g/t; the pulp environment has a pH of 9. The operation is implemented as in fig. 1, for example, the pH of the pulp in the flotation process is 9; the dosage of the flotation reagent is 45 g/t; the mineral was an artificial blend (see Table 1; 2 g).
Table 8 shows the results of example 7
TABLE 8
In table 8, the grade and recovery rate of lead in the concentrate reach 81.34% and 93.31, the grade and recovery rate of zinc are only 4.08% and 6.03%, and galena and sphalerite are almost completely separated, which shows that the flotation agent in the invention has excellent selective collecting performance.
Example 8
The effect of the unique structure of the compound shown in the formula 1 in flotation separation is verified by adopting an artificial mixed ore mode. We used galena and blende in south of Hunan, using the procedure shown in FIG. 1. The optimal reagent system and flotation environment are adopted (95 parts of flotation reagent collecting agent, wherein the ratio of formula 1 (variable) to formula 2 is 10: 85, 5 parts of foaming agent, the concentration of flotation reagent is 45g/t, the pH value of ore pulp environment is 9;). Except for the change of the compound of the formula 1 in the flotation reagent, the types of other reagents are not changed.
The operation is implemented as in fig. 1, for example, the pH of the pulp in the flotation process is 9; the dosage of the flotation reagent is 45 g/t; the mineral was an artificial blend (see Table 1; 2 g).
Table 9 shows the recovery of galena and sphalerite in different formulas 1.
TABLE 9
The results in Table 9 show that the molecular structure of the first-order N-N-CS-O (N) in the molecule of the formula 1 and the cooperative control of active hydrogen are key to realize intramolecular cooperation, improve the selective separation of galena and sphalerite and improve the recovery rate and grade of the galena, and the separation efficiency of the compound without adopting the structure is greatly reduced in the case, wherein the compound which is already applied in industry is a white drug
The recovery rate and grade of galena in the concentrate are only 59.87 percent and 80.11 percent, while the recovery rate and grade of sphalerite are 20.71 percent and 35.77 percent; compared with the compound shown in the formula 1-D, the recovery rate and the grade of the concentrate galena reach 78.76% and 93.48%, while the recovery rate and the grade of the sphalerite are only 6.14% and 9.42%, which shows the excellent selective collecting effect of the flotation reagent.
Example 9
To verify the effect of the compounds of formula 1 and 2 alone on the flotation recovery of artificial mixed ore. Flotation tests were carried out using galena and sphalerite in Hunan, using the procedure shown in FIG. 1, using the optimum chemical regime and flotation environment (95 parts of flotation chemical collector (formula 1 or formula 2 alone), 5 parts of foaming agent, concentration of flotation chemical: 45g/t, pH 9 in pulp environment).
The operation is implemented as in fig. 1, for example, the pH of the pulp in the flotation process is 9; the dosage of the flotation reagent is 45 g/t; the collector composition is shown in table 10; the mineral was an artificial blend (see Table 1; 2 g).
Table 10 shows the recovery rates of mixed minerals when the compounds of formula 1 and 2 were used alone.
Watch 10
Table 10 shows that the compounds of formula 1 and 2 alone did not achieve, or even differed, the effect of the combination. Particularly, when the compound shown in the formula 2 is used alone, the recovery rate of lead and zinc in the concentrate is almost simultaneously over 80 percent, and the compound has no selective capability. It is shown that the combined use of the compound of formula 1 and the compound of formula 2 is one of the keys to the selective separation of lead and zinc.
Example 10
In order to verify the unique influence of the compound in the formula 2 in the flotation reagent B on the flotation recovery rate, the plumbum ore and the sphalerite in Hunan are adopted, the flow shown in the figure 1 is adopted, and the optimal reagent system and the optimal flotation environment are adopted (95 parts of flotation reagent collecting agent, wherein the ratio of the formula 1 (1-C +1-D (the mass ratio is 1: 1)) to the component B (sodium ethylxanthate or black powder) is 10: 85, 5 parts of foaming agent, the concentration of the flotation reagent is 45g/t, and the pH value of an ore pulp environment is 9;). The test is divided into two groups, and a black drug (specifically sodium di-sec-butyldithiophosphate) complex reagent is used as a flotation reagent to be compared with the flotation reagent. The flotation process parameters were the same for each group of cases, differing only in the flotation reagent.
The operation is implemented as in fig. 1, for example, the pH of the pulp in the flotation process is 9; the dosage of the flotation reagent is 45 g/t; the compositional proportions of the collectors are shown in table 11; the mineral was an artificial blend (see Table 1; 2 g).
Table 11 shows the results of example 10.
TABLE 11
Table 11 shows that lead and zinc can be almost completely separated using the compound of formula 2; after the black powder is used for replacing the compound of the formula 2, the grade and the recovery rate of lead in the concentrate are reduced by 15.49 and 17.33 percentage points, and the grade and the recovery rate of zinc are increased by 12 and 17.91 percentage points, which shows that the compound of the formula 2 is also the key for separating lead and zinc in the flotation reagent.
Example 11
In order to verify the influence of the proportion of the compound reagent on the flotation recovery rate of the artificial mixed ore, the plumbum galenite and the sphalerite in Hunan are adopted, the flow shown in the figure 1 is adopted, and the flotation is carried out by changing the proportion of the compound of the formula 1 (the formula 1-C + the formula 1-D (the mass ratio is 1: 1)) and the compound of the formula 2 (sodium ethylxanthate) by adopting the optimal reagent system and the optimal flotation environment (95 parts of the flotation reagent collecting agent, 5 parts of the foaming agent, 45g/t of the flotation reagent concentration and 9 ℃ in the pulp environment).
The operation is implemented as in fig. 1, for example, the pH of the pulp in the flotation process is 9; the dosage of the flotation reagent is 45 g/t; the compositional proportions of the collectors are shown in table 12; the mineral was an artificial blend (see Table 1; 2 g).
Table 12 shows the recovery of mixed minerals when the compounds of formula 1 and 2 were used in different proportions.
TABLE 12
Table 12 shows that the ratio of the compound of formula 1 to the compound of formula 2 has a great influence on the synergistic effect of the combination, and the separation efficiency of lead and zinc is high in the ratio of the medicament of the invention, and the separation can not be achieved after the ratio is exceeded.
Example 12
In order to verify the influence of pH on the flotation recovery rate of the artificial mixed ore in the invention, galena and sphalerite in Hunan are adopted, the flow shown in FIG. 1 is adopted, and flotation is carried out by changing the pH of ore pulp by adopting an optimal chemical system (95 parts of flotation chemical collectors, the ratio of compounds of formula 1 (formula 1-C + formula 1-D (mass ratio of 1: 1)) to compounds of formula 2 (sodium ethylxanthate) is 10: 85, 5 parts of foaming agents, the concentration of flotation chemicals is 45 g/t; and the like).
The operation is carried out in the same way as that shown in figure 1, for example, the dosage of the flotation reagent is 45 g/t; the pulp pH is shown in Table 13; the mineral was an artificial blend (see Table 1; 2 g).
Table 13 shows the data for flotation agents at different pH for mixed minerals.
Watch 13
Table 13 shows that the flotation agent of the present invention performed well in the full pH environment studied. Wherein, the flotation separation effect is best under the alkalescent condition. Even under the condition of strong acid with poor effect, the grade and recovery rate of lead in the concentrate can be kept above 70% and 84%, and the grade and recovery rate of zinc can be kept below 20% and 13%, thus fully showing the excellent performance of the flotation reagent.
Claims (10)
1. A flotation reagent for selectively separating galena and sphalerite, comprising a reagent a and a reagent B;
the medicament A is at least one of compounds with the structural formula 1;
the medicament B is at least one of compounds with the structural formula of formula 2;
R1is H, C1～C3Alkyl of (C)5～C15Saturated cycloalkyl, phenyl, benzyl or acyl;
y is R2-O-*
Said R2Is C1～C6Alkyl, phenyl or benzyl of (a); said R3Is H or C1～C6Alkyl groups of (a); r4Is H, amino, C1～C6Alkyl of (a) or-N-R; r is C1～C3Alkyl groups of (a); and in formula 1, the atomic percentage of the N heteroatom is greater than or equal to 15%;
R5is C1～C15Alkyl of (C)5～C15Saturated cycloalkyl, phenyl or benzyl of (a);
and M is an alkali metal element or ammonium ion.
2. The flotation reagent for selective flotation separation of galena and blende according to claim 1, wherein R is1Is H, C1～C3Alkyl of (C)2～C4Acyl group of (4); further preferably H or acetyl;
preferably, R is2Is C1～C3Alkyl groups of (a);
preferably, R3Is H or C1～C3Alkyl groups of (a); r4Is H, amino or C1～C3Alkyl groups of (a);
preferably, in formula 1, the atomic percentage of the N heteroatom is 10-55%.
3. The flotation reagent for selective flotation separation of galena and blende according to claim 1, wherein said reagent a is a mixture of two or more compounds of the following formulae 1-a to 1-D;
4. the flotation reagent for selective flotation separation of galena and blende according to claim 1, wherein R is the one in which R is a salt of zinc5Is C2～C6Alkyl groups of (a);
preferably, M is Na or K.
5. The flotation reagent for selective flotation separation of galena and blende according to claim 1, wherein the amount of the reagent a is 5 to 50 parts by weight, more preferably 10 to 30 parts by weight; more preferably 10 to 15 parts;
45-90 parts of medicament B; preferably 65-80 parts; more preferably 80 to 85 parts.
6. The agent for the selective flotation separation of galena and blende according to any one of claims 1 to 5, further comprising a foaming agent;
preferably, the foaming agent is one of 2# oil, 4# oil, polyethylene glycol dibenzyl ether (glycerol benzyl oil), polypropylene glycol alkyl ether or W-02 foaming agent;
further preferably, the foaming agent is not more than 10 parts by weight; preferably 3 to 5 parts.
7. A selective flotation separation method for galena and sphalerite is characterized in that the flotation agent of any one of claims 1 to 6 is used for mixed ore containing galena and sphalerite to carry out flotation, and concentrate enriched with galena and tailings enriched with sphalerite are obtained.
8. The flotation separation method of galena and blende according to claim 7, wherein the pH of the ore pulp in the flotation process is 3-12; preferably 5 to 11; more preferably 8 to 10.
9. The flotation separation method for galena and blende according to claim 7, wherein the amount of the flotation agent is 40 to 50 g/t; further preferably 45 to 50 g/t.
10. The method for flotation separation of galena and blende according to any one of claims 7 to 9, wherein the mixed ore is lead-zinc sulfide ore.
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