CN108246511B - Calcium carbonate inhibitor for fluorite beneficiation and preparation method thereof - Google Patents
Calcium carbonate inhibitor for fluorite beneficiation and preparation method thereof Download PDFInfo
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- CN108246511B CN108246511B CN201810030390.5A CN201810030390A CN108246511B CN 108246511 B CN108246511 B CN 108246511B CN 201810030390 A CN201810030390 A CN 201810030390A CN 108246511 B CN108246511 B CN 108246511B
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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 discloses a calcium carbonate inhibitor for fluorite ore dressing and a preparation method thereof, and the calcium carbonate inhibitor comprises sulfate, dextrin and ABS components in parts by weight: dextrin, ABS and sulfate are 1: 0.1-2: 0.5-3. The preparation method and the application are as follows: adding water into a container, slowly adding sulfate, dextrin and ABS in sequence, and stirring while adding to completely dissolve. When in use, the raw ore is added according to the proportion of 500-800 g/t of the total weight of active ingredients of dextrin, ABS and sulfate during the mineral roughing; if the content of calcium carbonate is too high, the calcium carbonate can be added in the second concentration and/or the fourth concentration according to the proportion of 200g/t of raw ore by the total weight of active ingredients of dextrin, ABS and sulfate. By using the inhibitor, calcium carbonate minerals with the content of 5-20% or higher in fluorite raw ores can be inhibited into tailings, so that the content of calcium carbonate in concentrate is controlled within 1%, and the recovery rate is improved to more than 80%; the grade of the concentrate is more than 97 percent; no corrosion to equipment; meanwhile, the inhibitor is degradable and has no pollution to water and environment.
Description
The technical field is as follows:
the invention belongs to the field of fluorite beneficiation, and particularly relates to a calcium carbonate inhibitor for fluorite beneficiation and a preparation method thereof.
Background art:
the overproof calcium carbonate content of fluorite ore dressing concentrate is a great problem influencing fluorite production for a long time, and the problem which cannot be solved for a long time in the industry has existed for decades. The fluorite ore associated with carbonate minerals is extremely widely distributed in Xinyang, Gansu Jiuquan and Anhui Guangde of Henan of China, and the areas are also main producing areas of fluorite of China, and most fluorite mines in the areas have the condition more or less.
According to the national standard, the content of calcium carbonate in the first-grade acid-grade fluorite powder is not more than 1 percent. At present, the following measures are taken in production:
1. blending, namely doping raw fluorite ore without calcium carbonate, controlling the content of calcium carbonate in the ore to be 3-5%, adding sulfuric acid, acidified water glass and the like during flotation operation, and inhibiting the part of calcium carbonate, wherein the method seriously corrodes equipment, and a large amount of waste sulfuric acid is contained in tailings to pollute the environment; and the crude calcium carbonate is slightly high, so that the inhibition is ineffective, and the added sulfuric acid can inhibit fluorite, so that the recovery rate is reduced.
2. Hydrochloric acid is added into the concentrate pool, so that calcium carbonate entering the concentrate becomes water-soluble calcium chloride, and is removed along with the filtering and dewatering operations. In order to reach the reaction concentration, a large amount of fuming hydrochloric acid is needed, the filtered wastewater passes through the field of meadow and is difficult to grow and acid gas is forced, so the production completely does not meet the national environmental protection requirement, and the plant selection is often reinvested by the environmental protection department to stop production. But under the drive of interests, manufacturers try to avoid theft, and serious pollution is caused in the areas for decades. The national non-metal mine association and the fluorite professional committee are required to be involved and attacked by colleges, scientific research institutions and industrial and mining enterprises after being opened for many times, and the national non-metal mine association and the fluorite professional committee are used for solving the problems without really applying to production though a plurality of reported papers are passed for decades.
At present, the domestic patent database also has some published documents about the fluorite mine carbonate inhibitor:
the invention discloses a flotation separation method of low-grade fluorite barite, which adopts water glass as an inhibitor of siliceous minerals and calcium carbonate minerals, oleic acid as a collector of fluorite and barite, and starch, sodium sulfate, hydrochloric acid and sodium hexametaphosphate as the inhibitor of the barite minerals. The method aims at solving the separation of fluorite and barite, and can only be used for ores with raw ore carbonate content lower than 4%.
The invention discloses a fluorite ore carbonate inhibitor and a preparation method thereof, wherein the inhibitor comprises four components of acid, water glass, aluminum sulfate and tannin extract. The inhibitor is mainly used for sorting quartz vein type fluorite ores with low carbonate content, the dosage needs to be strictly controlled, and the inhibitor can inhibit fluorite slightly, so that the recovery rate is seriously reduced.
The crux of the problem is that fluorite beneficiation is a calcium beneficiation process. Fluorite (CaF)2) Containing Ca2+Calcium carbonate also contains Ca2+The collector and regulator for fluorite ore dressing are also carbonate mineral collector and regulator. At present, no single collector for catching fluorite and not collecting calcium carbonate exists, which is the reason that calcium carbonate is difficult to inhibit during fluorite ore dressing.
Carbonate minerals refer mineralogically to a class of minerals, not to one. Calcium carbonate minerals alone are typically calcite, limestone, dolomite, aragonite, and the like. Meanwhile, siderite (iron carbonate) and magnesite (magnesium carbonate) are common carbonate minerals, have the flotation characteristic of the calcium carbonate minerals and are extremely easy to collect by oleic acid. These minerals are both common and distinct, and complete inhibition of all of them with one agent is clearly not possible. It is determined that a plurality of formulas or a plurality of medicaments respectively inhibit related components, the problem is difficult to solve by the strength of a selected factory, and the research department of the country does not invest huge resources and spend a great deal of time and energy to research the research subject with limited application range, so that the problem cannot be solved for a long time.
In recent years, along with the development of fluorite industry, more and more factories are built, more and less easy-to-select ores are available, more and more high-quality fluorite ores are closed due to resource exhaustion, and abandoned mines with too high carbonate content are re-mined due to resource shortage, so that the problem that the fluorite production is influenced by the overproof calcium carbonate content of fluorite ore dressing concentrate is more and more prominent, and less factories can only produce low-grade fluorite due to the influence of calcium carbonate, which is a waste of national resources, and the situation makes the industry people have no help and very pain.
In summary, the calcium carbonate inhibitor for fluorite mineral separation adopted in the prior art has a certain inhibiting effect on typical calcium carbonate minerals, and when the content of raw ore calcium carbonate is lower than 3% -5%, the content of concentrate calcium carbonate can be controlled within the national standard level of 1%, but when the content of raw ore calcium carbonate is higher than 3% -5%, some of the existing agents can strongly inhibit fluorite, and some of the existing agents cannot exert the due effect in an oleic acid flotation system, so that the environmental pollution is serious, and resources are wasted.
The invention content is as follows:
the invention aims to solve the technical problem of providing a calcium carbonate inhibitor for fluorite ore dressing and a preparation method thereof, which can control the content of calcium carbonate in concentrate within 1% and improve the recovery rate to more than 80% when the content of calcium carbonate in raw ore is 5% -20% or even higher, so that the grade of the concentrate reaches more than 97%; no corrosion to equipment; meanwhile, the inhibitor is degradable and has no pollution to water and environment.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a calcium carbonate inhibitor for fluorite ore dressing contains sulfate, dextrin and ABS component.
Preferably, the dextrin is yellow dextrin.
Preferably, the sulfate salt is sodium sulfate.
Preferably, the weight ratio of the components is dextrin, ABS and sulfate is 1: 0.1-2: 0.5-3.
More preferably, the weight ratio of the components is dextrin to ABS to sulfate is 1: 0.2: 1.
The invention also provides a preparation method of the calcium carbonate inhibitor for fluorite beneficiation, which comprises the following steps: the dextrin, the ABS and the sulfate are weighed according to the proportion, water is put into a container, the sulfate, the dextrin and the ABS are sequentially and slowly added and stirred simultaneously to be completely dissolved, and the prepared calcium carbonate inhibitor water solution for fluorite ore dressing contains 8-15 percent of the total weight of the dextrin, the ABS and the sulfate.
The invention relates to the application of calcium carbonate inhibitor for fluorite ore dressing, which comprises the following steps: according to the proportion of active ingredients of dextrin, ABS and sulfate accounting for 500-800 g/t of the total weight of raw ore, the prepared aqueous solution containing dextrin, ABS and sulfate is added during the mineral roughing, namely, the total weight of the dextrin, ABS and sulfate in the calcium carbonate inhibitor aqueous solution for fluorite ore dressing is 500-800 g added into each ton of raw ore. If the content of calcium carbonate is too high, the calcium carbonate inhibitor water solution for fluorite ore dressing can be added according to the proportion of 200g/t raw ore by the total weight of active ingredients of dextrin, ABS and sulfate during the second time of ore dressing and/or the fourth time of ore dressing.
The inhibitor is a kind of medicament which helps mineral hydrophilicity in terms of the principle, and the problem to be solved is that the inhibitor has adsorbability to the mineral to be removed and has stronger selectivity; and secondly, the paint has wettability and is hydrophilic and oleophobic after being combined with carbonate minerals.
The active group of the yellow dextrin selected by the invention is hydroxyl, and can be combined with calcium ions in calcium carbonate, so that the aims of shielding the calcium ions and preventing the calcium ions from being combined with oleic acid and floating up in a hydrophobic manner are fulfilled. However, with the increase of the content of calcium carbonate, the inhibition capacity of dextrin is not increased any more, analysis is caused by insufficient hydrophilicity of dextrin, and under the condition that a large amount of carbonate minerals and oleic acid exist, the required hydrophilic and oleophobic effects are difficult to achieve, so that the enhancement of the hydrophilicity of dextrin is one of the methods for solving the problems.
The surfactant has the function of infiltrating solid particles, and on the basis of a large number of experiments, sodium dodecyl benzene sulfonate (ABS for short) is selected, and a small amount of ABS is added into dextrin, so that the hydrophilicity can be greatly enhanced, and the inhibition force is greatly improved.
The invention aims at solving the problems that the fluorite raw ore with the calcium carbonate content of 5-20 percent or higher is difficult to adopt a preferential flotation method due to the difficulty of separation, the calcium carbonate is separated out firstly, common carbonate minerals have little economic value and can only be inhibited into tailings during beneficiation, so the requirement on an inhibitor is high, the fluorite beneficiation requirement with the high calcium carbonate content is still difficult to meet only by dextrin and a surfactant, on the other hand, the floating of certain calcium carbonate minerals is that the surfaces are polluted by metal ions such as iron, aluminum and the like due to impurity, and the oleic acid has certain collecting property on the metal ions by collecting Fe3+、Al2+The calcium carbonate mineral is brought up. In order to solve the problem, a complexing method is adopted to eliminate the metal ions and change the metal ions into metal complexes, various complexing reagents are subjected to screening tests, and the sodium sulfate is found to have good use effect. On the basis of a large number of laboratory and factory selection tests, the invention creatively combines sulfate, dextrin and ABS groupsThe combination of three agents greatly improves the selectivity of the inhibitory power of the inhibitor.
The invention has the following beneficial effects:
by using the inhibitor, calcium carbonate minerals with the content of 5-20% or higher in fluorite raw ores can be inhibited into tailings, so that the content of calcium carbonate in concentrate is controlled within 1%, and the recovery rate is improved to more than 80%; the grade of the concentrate is more than 97 percent; no corrosion to equipment; meanwhile, the inhibitor is degradable and has no pollution to water and environment. The inhibitor can be used for enterprises with long-term products which do not reach the standard to produce qualified products, the products are nontoxic and tasteless, three wastes are not discharged in the production process, no pollution is caused in the use process, and the inhibitor meets the national requirements for building green mines.
The specific implementation mode is as follows:
example 1
1. Dissolving: 40kg of dextrin, 8kg of ABS and 40kg of sodium sulfate are taken, and are slowly added into 1000kg of water according to the sequence of sulfate, dextrin and ABS while stirring, so that the dextrin, the ABS and the ABS are completely dissolved.
2. Use of: the solution is added into the crude fluorite ore for roughing according to the proportion of 800g/t of crude ore by the total weight of active ingredients of dextrin, ABS and sulfate.
For raw ore with high calcium carbonate content, the above solutions can be added into 2 and 4 concentrates respectively, and the ratio of 200g/t raw ore is calculated according to the total weight of active ingredients of dextrin, ABS and sulfate.
Example 2
1. Dissolving: 60kg of dextrin, 8kg of ABS and 40kg of sodium sulfate are taken, and are slowly added into 1000kg of water according to the sequence of sulfate, dextrin and ABS while stirring, so that the dextrin, the ABS and the ABS are completely dissolved.
2. Use of: the solution is added into the crude fluorite ore for roughing according to the proportion of 700g/t of crude ore by the total weight of active ingredients of dextrin, ABS and sulfate.
For raw ore with high calcium carbonate content, the above solutions can be added into 2 and 4 concentrates respectively, and the ratio of 200g/t raw ore is calculated according to the total weight of active ingredients of dextrin, ABS and sulfate.
Example 3
1. Dissolving: 80kg of dextrin, 8kg of ABS and 40kg of sodium sulfate are taken, and are slowly added into 1000kg of water according to the sequence of sulfate, dextrin and ABS while stirring, so that the dextrin, the ABS and the ABS are completely dissolved.
2. Use of: the solution is added into the crude fluorite ore for roughing according to the proportion of 500g/t of crude ore by the total weight of active ingredients of dextrin, ABS and sulfate.
For raw ore with high calcium carbonate content, the above solutions can be added into 2 and 4 concentrates respectively, and the ratio of 200g/t raw ore is calculated according to the total weight of active ingredients of dextrin, ABS and sulfate.
It should be noted that the calcium carbonate minerals contained in the ore are not the same as one, i.e. the inhibitor for inhibiting dolomite and the inhibitor for inhibiting calcite are not completely consistent in the formula components, so that the proportion is adjusted or other components are added according to the conditions when the calcium carbonate mineral is used until the satisfactory index is obtained.
Example 4
To test the effect of the calcium carbonate inhibitor for fluorite ore dressing, the CaF in the crude ore is adopted2
35.1% of CaCO3A calcium carbonate inhibitor for fluorite ore dressing prepared in example 1 was used to perform an effect comparison experiment on a fluorite ore with a content of 19.82% in hengyang.
As can be seen from the above table: the calcium carbonate inhibitor for fluorite mineral separation can effectively inhibit carbonate in minerals, and can obtain a product with higher recovery rate and high quality.
Claims (8)
1. A calcium carbonate inhibitor for fluorite ore dressing is characterized in that: the fluorite ore dressing is fluorite raw ore with 5-20% of calcium carbonate content in the fluorite raw ore.
2. The fluorite calcium carbonate inhibitor for beneficiation according to claim 1, wherein: the dextrin is yellow dextrin.
3. The fluorite calcium carbonate inhibitor for beneficiation according to claim 1, wherein: the sulfate is sodium sulfate.
4. The calcium carbonate inhibitor for fluorite beneficiation according to any one of claims 1 to 3, characterized in that: the weight ratio of the components is as follows: dextrin, ABS and sulfate are 1: 0.1-2: 0.5-3.
5. The fluorite calcium carbonate inhibitor for beneficiation according to claim 4, wherein: the weight ratio of the components is as follows: dextrin, ABS and sulfate in the ratio of 1 to 0.2 to 1.
6. The method for preparing a calcium carbonate inhibitor for fluorite beneficiation according to any one of claims 1 to 5, characterized by: the dextrin, the ABS and the sulfate are weighed according to the proportion, water is put into a container, the sulfate, the dextrin and the ABS are sequentially and slowly added and stirred simultaneously to be completely dissolved, and the prepared calcium carbonate inhibitor water solution for fluorite ore dressing contains 8-15% of the total weight of the dextrin, the ABS and the sulfate.
7. Use of the calcium carbonate inhibitor for fluorite beneficiation according to any one of claims 1 to 5, characterized in that: adding a prepared aqueous solution containing dextrin, ABS and sulfate during mineral roughing according to the proportion of active ingredients of the dextrin, the ABS and the sulfate to raw ore of 500-800 g/t in total weight, wherein the fluorite beneficiation is the fluorite raw ore of which the content of calcium carbonate is 5-20% in the fluorite raw ore.
8. Use of the calcium carbonate inhibitor for fluorite beneficiation according to claim 7, characterized in that: according to the proportion of active ingredients of dextrin, ABS and sulfate accounting for 200g/t of the total weight of raw ore, the prepared aqueous solution containing dextrin, ABS and sulfate is further added during the second concentration and the fourth concentration.
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| CN111672637A (en) * | 2020-06-23 | 2020-09-18 | 山东大明精细化工有限公司 | Calcium carbonate inhibitor for fluorite beneficiation and preparation method thereof |
| CN114100842B (en) * | 2021-11-02 | 2023-10-17 | 湖南有色郴州氟化学有限公司 | Low-grade fluorite carbon-reduction silicon-reduction quality-improvement method |
| CN115007326B (en) * | 2022-04-06 | 2023-09-19 | 郴州市苏仙区黄泥坳矿业有限公司 | Flotation method of high-calcium tungsten fluorite ore |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103341414A (en) * | 2013-06-26 | 2013-10-09 | 烟台市富林矿山机械有限公司 | Inhibitor for beneficiation and manufacturing method for inhibitor |
| CN106179763A (en) * | 2016-06-27 | 2016-12-07 | 洛阳丰瑞氟业有限公司 | Fluorite flotation calcium carbonate inhibitor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103341414A (en) * | 2013-06-26 | 2013-10-09 | 烟台市富林矿山机械有限公司 | Inhibitor for beneficiation and manufacturing method for inhibitor |
| CN106179763A (en) * | 2016-06-27 | 2016-12-07 | 洛阳丰瑞氟业有限公司 | Fluorite flotation calcium carbonate inhibitor and preparation method thereof |
Non-Patent Citations (3)
| Title |
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| 周利华等.萤石浮选药剂研究现状与展望.《有色金属科学与工程》.2016,第7卷(第4期), * |
| 脂肪酸增效剂在浮选中的应用;李冬莲;《武汉化工学院学报》;19990930;第21卷(第3期);全文 * |
| 萤石浮选药剂研究现状与展望;周利华等;《有色金属科学与工程》;20160831;第7卷(第4期);第94-95页 * |
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