CN108704767B - Combined inhibitor and application thereof in separation of molybdenum-containing and other metal sulfide ores - Google Patents
Combined inhibitor and application thereof in separation of molybdenum-containing and other metal sulfide ores Download PDFInfo
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- CN108704767B CN108704767B CN201810497050.3A CN201810497050A CN108704767B CN 108704767 B CN108704767 B CN 108704767B CN 201810497050 A CN201810497050 A CN 201810497050A CN 108704767 B CN108704767 B CN 108704767B
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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
- B03D1/018—Mixtures of inorganic and organic 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
- B03D2201/06—Depressants
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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 belongs to the technical field of non-ferrous metal beneficiation, and particularly relates to a combined inhibitor and application thereof in separation of sulfide ores containing molybdenum and other metals. The invention utilizes the synergistic effect of the combined medicament, improves the effects of adsorption, chelation and inhibition on minerals, and effectively inhibits sulfide minerals containing bismuth, lead, antimony and the like. The inhibition effect of the inhibitor is stronger than that of a single inhibitor, so that the molybdenum can be selectively separated from other metal sulfide minerals, and the flotation index of the molybdenum concentrate is improved. In the flotation process, the combined inhibitor can be directly added, so that the operation is convenient. The combined inhibitor developed by the invention has the advantages of safe use, low dosage, low toxicity, environmental protection, no influence on subsequent selection operation and the like, and has very important significance for improving the comprehensive recycling of metal resources and the economic benefit of mines.
Description
Technical Field
The invention belongs to the technical field of non-ferrous metal beneficiation, and particularly relates to a combined inhibitor and application thereof in separation of sulfide ores containing molybdenum and other metals.
Background
Nonferrous metals are important industrial raw materials, and are widely applied in the fields of electric appliances, light industry, transportation, building industry, mechanical manufacturing, national defense industry and the like. Along with the continuous development of national economy in recent years, the demand and the daily increase of metal resources such as molybdenum, bismuth, copper, lead, antimony and the like exist, and meanwhile, the metal resources in China have the characteristics of serious imbalance in supply and demand, high external dependence, single import channel and the like. The method improves the self-sufficiency rate of nonferrous metal resources in China, and has important strategic and economic significance for maintaining reasonable and rapid development of the nonferrous metal industry.
At present, flotation separation of molybdenum and sulfide minerals such as copper, lead, bismuth, antimony, iron and the like is one of the problems which are always concerned by the ore dressing industry, and because the floatability of the sulfide minerals is usually similar and all the sulfide minerals belong to easily floating minerals, separation of metal sulfide minerals is usually difficult in production practice, and how to select a flotation reagent with high-efficiency inhibition effect is especially important for realizing effective separation of molybdenum and other metal sulfide minerals. The traditional mineral separation process in China adopts inhibitors such as sodium sulfide, cyanide, thioglycollic acid, lime and the like to realize the inhibition of sulfide minerals such as copper, lead, iron, bismuth, antimony and the like in a high-alkali system. However, high alkali conditions (pH >12, which is practical for industrial production) are detrimental to the flotation of part of the molybdenum ore, resulting in a reduced recovery of molybdenum from the molybdenum concentrate. Particularly, the high alkali is very unfavorable for the comprehensive utilization of low-grade complex porphyry type molybdenum-bismuth ore and molybdenum-bismuth-copper multi-metal sulfide ore accompanied with noble metal, and a large amount of associated valuable metal elements such as gold, silver, molybdenum and the like can be inhibited by the high alkali to enter sulfur concentrate, so that the effect of comprehensive recovery cannot be obtained, and the reduction of the comprehensive benefits of the mine and the loss of the noble metal are caused. In addition, a large amount of sodium sulfide is required under the high-alkali condition, so that the direct production cost of the mine is increased, and a large amount of high-alkali wastewater needs to be treated, thereby causing great harm to the environment. And cyanide and sodium sulfide are toxic inhibitors, and have potential hazards to the life health of the miners.
Engineering technicians in mines at home and abroad have also recognized the defects of a high-alkali process and the existing flotation inhibitor, and corresponding research work is carried out, so that a stable, efficient and nontoxic inhibitor is hopefully found under the condition of alkalescence or neutrality, and the efficient separation of molybdenum and other metal sulfide minerals is realized. At present, in the existing relevant literature data, the technology for separating molybdenum from other metal sulfide ores by using hydrogen peroxide and gallic acid as combined inhibitors is rarely reported.
Disclosure of Invention
The invention aims to provide a combined inhibitor which can be used under the condition of alkalescence or neutrality, is efficient and environment-friendly, has wide sources, small dosage and good stability, and can efficiently separate molybdenum and other metal sulfide ores.
The present invention is a combination inhibitor; the combination inhibitor comprises hydrogen peroxide and gallic acid. The molecular formula of the hydrogen peroxide is H2O2The molecular formula of the gallic acid is C7H6O5The chemical structural formula of the hydrogen peroxide is as follows:
the chemical structural formula of the gallic acid is as follows:
the present invention is a combination inhibitor; the mass ratio of the hydrogen peroxide to the gallic acid in the combined inhibitor is 2-6: 8-4, preferably 5-6: 4-5.
Preferably, the present invention relates to a combination inhibitor; the combination inhibitor is composed of hydrogen peroxide solution and gallic acid solution.
Preferably, the present invention relates to a combination inhibitor; the hydrogen peroxide and the gallic acid in the combined inhibitor can be used in the form of any one of pure solid, pure liquid and solutions with different concentrations.
Preferably, the invention relates to the application of the combined inhibitor in separating sulfide ore containing molybdenum and other metals; the implementation scheme is as follows: the method comprises the following steps of taking minerals of sulfide containing molybdenum and other metal sulfides as raw materials, and controlling the pH value of a flotation system to be 1-14, preferably 6-10, and further preferably 8-9 in the flotation process; hydrogen peroxide and gallic acid are used as flotation inhibitors of other metal sulfides to carry out flotation separation of molybdenum sulfide and other metal sulfides.
Preferably, the invention relates to the application of the combined inhibitor in separating sulfide ore containing molybdenum and other metals; (ii) a The method inhibits the flotation of other metal sulfide ores in the flotation process, and achieves the purpose of separating molybdenum and other metal sulfide ores. The other metal sulfide is at least one selected from bismuth glorious ore, bismuth blister ore, rhombohedral bismuth ore, copper bismuth ore, galena, chromite, stibnite, vermilion silver ore, stibnite, jamesonite, and stibnite.
Preferably, the invention relates to the application of the combined inhibitor in separating sulfide ore containing molybdenum and other metals; (ii) a The combined inhibitor can be used for any one of the flotation operations of roughing operation, concentration operation and scavenging operation.
Preferably, the invention relates to the application of the combined inhibitor in separating sulfide ore containing molybdenum and other metals; (ii) a The combined inhibitor can be added into the flotation pulp separately or after being mixed.
Preferably, the invention relates to the application of the combined inhibitor in separating sulfide ore containing molybdenum and other metals; the total dosage range of the combined inhibitor in the roughing operation is 200-1500 g/ton ore feeding, preferably 200-; exceeding this range will destroy the floatability of the mineral, resulting in a decrease in the recovery of valuable metals.
Preferably, the invention relates to the application of the combined inhibitor in separating sulfide ore containing molybdenum and other metals; the total dosage range of the combined inhibitor in the concentration operation is 50-500 g/ton ore feeding, preferably 50-300 g/ton ore feeding, and further preferably 50-150 g/ton ore feeding, and if the dosage is lower than the range, the inhibition effect is possibly insufficient, and minerals cannot be separated; exceeding this range will destroy the floatability of the mineral, resulting in a decrease in the recovery of valuable metals.
Preferably, the invention relates to the application of the combined inhibitor in separating sulfide ore containing molybdenum and other metals; the total dosage range of the combined inhibitor in scavenging operation is 50-300 g/ton ore feeding, preferably 50-200 g/ton ore feeding, and further preferably 50-100 g/ton ore feeding, and if the dosage is lower than the range, the inhibiting effect is insufficient, and minerals cannot be separated; exceeding this range will destroy the floatability of the mineral, resulting in a decrease in the recovery of valuable metals.
In the beneficiation process, the fineness of the raw materials, the dosage system of the collecting agent and the foaming agent and the control of related parameters in the prior art can be consistent.
The hydrogen peroxide, the gallic acid and the like adopted by the invention belong to conventional reagents sold in the market.
Compared with the prior inhibitor for flotation separation of molybdenum and other metal sulfide ores, the technical scheme of the invention has the following beneficial effects:
⑴ the invention discloses a combined inhibitor for separating molybdenum and other metal sulfide ores, which is used for separating molybdenum and other metal sulfide ores in an ore pulp system with the pH value of 8-9, so that a high-alkali system is replaced and the separation efficiency is improved.
⑵ the invented composite depressor can be widely used in the flotation process flows of preferential flotation, mixed flotation, etc. it has the advantages of strong selectivity, small dosage of chemical, simple chemical system, no influence on the subsequent selection operation, greatly reducing the production cost and increasing the utilization rate of mineral resources.
⑶ the molybdenum-bismuth separation combined inhibitor hydrogen peroxide + gallic acid disclosed by the invention is a stable, efficient, safe and low-toxicity inhibitor, is environment-friendly, convenient to treat, stable in flotation process, easy to control and has very important significance for improving comprehensive recycling of metal resources and economic benefits of mines.
Drawings
FIG. 1 is a flow chart of a beneficiation process of a combined inhibitor applied to molybdenum bismuth sulfide ores.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
1. Mineral raw material
The selected molybdenum-bismuth sulfide ore contains 0.9-1.0% of molybdenum, 0.4-0.5% of bismuth, molybdenum mainly is molybdenite, and bismuth mainly is bismuthyl ore.
2. The operation steps and technical conditions are as follows:
① roughing operation, weighing a certain amount of molybdenum-bismuth ore, adding water to adjust the concentration of the ore pulp to be 30-35%, pouring the ore pulp into a proper flotation tank, adjusting the pH value of the ore pulp to be 8-9, adding 300g/t of collecting agent ethidium-sulfur-nitrogen and 50g/t of kerosene into the flotation tank, stirring for 3-5 minutes, adding 25g/t of foaming agent pine alcohol oil, stirring for 3 minutes, then performing molybdenum-bismuth mixed roughing operation to obtain mixed rough concentrate and tailings, and performing 2 times of blank scavenging on the tailings to obtain final tailings;
② separating molybdenum and bismuth, namely adding 500g/t of the combined inhibitor (wherein the mass ratio of hydrogen peroxide to gallic acid is 5: 5) into the mixed rough concentrate, stirring for 2-5 minutes, and then separating molybdenum and bismuth;
③ molybdenum concentration step, namely adding 150g/t of combined inhibitor (wherein the mass ratio of hydrogen peroxide to gallic acid is 5: 5) into the concentrate obtained in the molybdenum-bismuth separation operation, stirring for 3-5 minutes, adding 20g/t of kerosene, stirring for 3-5 minutes, and then performing molybdenum concentration step;
④ molybdenum concentration II, namely adding 50g/t of combined inhibitor (wherein the mass ratio of hydrogen peroxide to gallic acid is 5: 5) into the concentrate obtained in the molybdenum concentration I operation, stirring for 2-3 minutes, then adding 20g/t of kerosene, stirring for 2-3 minutes, and then performing the molybdenum concentration II operation;
⑤ molybdenum concentration for three to six times, namely stirring the concentrate obtained in the second molybdenum concentration operation for 2 to 3 minutes, and then carrying out blank concentration operation for 3 times to obtain the final concentrate which is the molybdenum concentrate;
⑥ molybdenum scavenging I, namely adding 15g/t of kerosene into the tailings of the molybdenum-bismuth separation operation at the same time, stirring for 2-3 minutes, then adding 15g/t of pine oil serving as a foaming agent, stirring for 2-3 minutes, and then performing molybdenum scavenging I;
⑦, sweeping second to fifth molybdenum, namely adding 15g/t of kerosene into the tailings in the first molybdenum sweeping operation, stirring for 2-3 minutes, and then carrying out blank sweeping operation for 3 times, wherein the final tailings are bismuth concentrate;
⑧ the middlings in the flotation operation of the molybdenum concentration section and the bismuth concentration section return to the previous flotation operation in sequence.
The results of the experiment are shown in table 1.
Example 2
The other conditions were identical to those of example 1, except that the maximum amount of the combination inhibitor of the invention was 1500g/t (wherein the mass ratio of hydrogen peroxide to gallic acid was 5: 5) at step ②, and 500g/t at steps ③, ④, the results of which are shown in Table 1.
Example 3
The other conditions were identical to those of example 1, except that a minimum dosage of 200g/t of the combined inhibitor of the invention was added in step ② (wherein the mass ratio of hydrogen peroxide to gallic acid was 5: 5), and a minimum dosage of 50g/t of the combined inhibitor of the invention was added in steps ③, ④, the results of which are shown in Table 1.
Comparative example 1
The other conditions were the same as in example 1 except that: during the flotation, only gallic acid was used as an inhibitor (the amount of gallic acid was equal to the amount of hydrogen peroxide + gallic acid in example 1), and the results are shown in table 1.
Comparative example 2
The other conditions were the same as in example 1 except that: the agent dosage of the combined depressant in the molybdenum-bismuth separation operation in the flotation process is 3000g/t, and the results are shown in table 1.
Comparative example 3
The other conditions were the same as in example 1 except that: the agent dosage of the combined depressant in the first and second molybdenum concentration stages in the flotation process was 1000g/t, and the results are shown in table 1.
Comparative example 4
The other conditions were the same as in example 1 except that: the results of the flotation process, in which the combined depressants were replaced with equal amounts of sodium sulfide, are shown in table 1.
TABLE 1 flotation test results
The experimental result of the embodiment 1 shows that the inhibitor obtained by the invention has good inhibition effect on bismuth sulfide ore, and is suitable for flotation separation of molybdenum-containing sulfide ore and other metal sulfide ore. Meanwhile, according to the experimental results of comparative examples 1-3, the dosage range of the combined inhibitor of the invention is out of the protection range of the invention or the single component medicament can not realize the inhibition effect on the sulfide ores such as copper, lead, iron, bismuth, antimony and the like. As can be seen from comparative example 4, the inhibitor of the present invention can achieve a better inhibiting effect than the inhibitors for molybdenum and other metal sulfide ores in the prior art beneficiation.
It should be noted that although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
1. The use of a combination inhibitor for the separation of molybdenum and other metal bearing sulphide ores; the method is characterized in that: the mass ratio of the hydrogen peroxide to the gallic acid in the combined inhibitor is 2-6: 8-4;
the flotation of other metal sulfide ores is inhibited in the flotation process, so that the aim of separating molybdenum from other metal sulfide ores is fulfilled; the other metal sulfide is at least one selected from bismuth glorious ore, bismuth soaking ore, rhombohedral bismuth ore, copper bismuth ore, galena, chromite, stibnite, vermilion silver ore, stibnite, jamesonite and stibnite; in the flotation process, controlling the pH value of a flotation system to be 1-14;
the combined inhibitor is used for at least one operation flow of roughing operation, fine selection operation and scavenging operation;
the total dosage range of the combined inhibitor in the roughing operation is 200-1500 g/ton ore feeding;
the total dosage range of the combined inhibitor in the concentration operation is 50-500 g/ton ore feeding;
the total dosage range of the combined inhibitor in scavenging operation is 50-300 g/ton ore feeding.
2. Use of a combination of inhibitors according to claim 1 for the separation of molybdenum and other metal bearing sulphide ores; the method is characterized in that: the mass ratio of the hydrogen peroxide to the gallic acid in the combined inhibitor is 5-6: 4-5.
3. Use of a combination of inhibitors according to claim 1 for the separation of molybdenum and other metal bearing sulphide ores; the method is characterized in that: and in the flotation process, the pH value of the system is controlled to be 6-10.
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| CN110280385A (en) * | 2019-06-17 | 2019-09-27 | 江西大吉山钨业有限公司 | A kind of tungsten ore association molybdenum bismuth sulphide ore without cyanogen beneficiation method |
| CN112403685B (en) * | 2020-10-26 | 2022-03-01 | 中南大学 | Flotation method for talc-containing molybdenum-zinc ore |
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| US3239461A (en) * | 1959-12-29 | 1966-03-08 | Sebba Felix | Ion flotation method |
| CN1365857A (en) * | 2001-01-18 | 2002-08-28 | 中南大学 | Ore dressing chemical prepared from tea leaf |
| CN105817342A (en) * | 2016-03-21 | 2016-08-03 | 中南大学 | Preparation method and application of non-molybdenum sulfide mineral flotation and separation inhibitor |
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| CN107309078A (en) * | 2017-08-16 | 2017-11-03 | 江西铜业股份有限公司 | A kind of copper-cobalt ore dressing method of the copper concentrate containing molybdenum |
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| US3239461A (en) * | 1959-12-29 | 1966-03-08 | Sebba Felix | Ion flotation method |
| CN1365857A (en) * | 2001-01-18 | 2002-08-28 | 中南大学 | Ore dressing chemical prepared from tea leaf |
| CN105817342A (en) * | 2016-03-21 | 2016-08-03 | 中南大学 | Preparation method and application of non-molybdenum sulfide mineral flotation and separation inhibitor |
| CN106179766A (en) * | 2016-08-09 | 2016-12-07 | 北京矿冶研究总院 | Molybdenum-lead separation inhibitor and preparation method and application thereof |
| CN107309078A (en) * | 2017-08-16 | 2017-11-03 | 江西铜业股份有限公司 | A kind of copper-cobalt ore dressing method of the copper concentrate containing molybdenum |
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