CN102921551B - Fluorite mineral flotation method - Google Patents
Fluorite mineral flotation method Download PDFInfo
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Abstract
The invention discloses a fluorite mineral flotation method. A flotation process of one-segment rough flotation plus scavenging and seven-segment fine flotation is matched with adoption of inhibitors formed by combination of water glass and sodium fluoride, and collecting agents formed by compounding of fatty acid and dimethyl formamide. In the flotation process, fluorites and other minerals in common fluorite minerals, complex fluorite minerals, flotation tailings containing the fluorites, and the like can be effectively separated, and obtained fluorite concentrate products are good in quality and have few impurities. The fluorite mineral flotation method is especially applicable to flotation separation of a large quantity of low-grade fluorite minerals with higher carbonate content, can be used for reducing the content of the impurities in beneficiation products, and has enormous economic benefits and environmental benefits.
Description
Technical field
The present invention relates to a kind of mineral separation process method, specifically a kind of flotation separation method of fluorite ore.
Background technology
Fluorite is a kind of strategic mineral, it plays a part very large to a national economic development, distributes extremely extensive all over the world, and in China for a long time as one of Dominant Mineral Resources product of exporting goods and earning foreign currency, it is of many uses, can be used for the industry such as metallurgy, chemical industry, pottery, cement, glass.
The total feature of China's flworite resources is that lean ore is many, rich ore is few, and many, the easy ore dressings of difficult ore dressing are few, and many, the single ore deposits of mineral intergrowth are few.All the year round, mineral processing in China technological equipment falls behind, and technical merit is low, and nonmetallic minerals recovery rate is only 20-40%, in the more international same industry, and the low 10-20% percentage point of extraction level of mineral products.Processing of fluorspar ores medicament is still based on old three sample oleic acid, waterglass and soda ash.Because oleic acid is that organic matter is insoluble in water, often float on liquid level, bad dispersibility in oil droplet, oil droplet shape, seriously constrain its collecting to active ingredient in fluorite ore.In recent years, people start to carry out emulsification modification to oleic acid, improve the rate of recovery of active ingredient with this, though this makes moderate progress to the dispersibility of oleic acid, performance is also undesirable.For complicated fluorite ore and fluorite mine tailing, it is excessive that existing recovery process also exists production line fund input, and operating procedure is complicated, and organic efficiency is low, reclaims the problems such as poly-doped impurity in fluorite is a lot of.
Fluorite ore mainly contains 3 types: quartz-fluorite type, quartz-fluorite-barite type, quartz-fluorite-calcite type.Beneficiation method has gravity treatment, magnetic separation to obtain the fluorite concentrate of metallurgical grade, and relieving haperacidity level fluorite concentrate then obtains mainly through floatation.For based on quartz, the less silicates fluorite ore of carbonate mineral content, with oleic acid make collecting agent, sodium carbonate adjusts agent, waterglass just can realize being separated of fluorite and gangue with comparalive ease as the inhibitor of gangue.And for wanting containing the more carbonate fluorite ore of calcite the separation realizing fluorite, obtain high-quality acid level fluorite concentrate, and viable economically be but difficulty very.Because all contain identical Ca in the lattice of these two kinds of mineral of calcite and fluorite
2+, thus make the surface physics of these two kinds of mineral and chemical property similar, its behavior acting on the collecting agent of these two kinds of mineral surfaces and inhibitor is similar, is difficult to realize calcite and is separated with the economical and efficient of fluorite.
Realize being separated of calcite and fluorite, be generally optimized from medicament and technique two aspect.What fluorite collecting agent was the most frequently used is oleic acid; The single adjusting agent of calcium mineral is suppressed generally to select waterglass, sodium metaphosphate, lignosulfonates, dextrin, tannic acid etc., but a lot of report shows, be used alone waterglass not strong to the inhibition of calcite, particularly when containing particulate calcite, fluorite is just more difficult with being separated of calcite.No. 157446, East Germany patent discloses a kind of N-methylamido carboxylic acid that adopts as the method for collecting agent sorting fluorite and calcite, can obtain CaF
297.3%, CaCO
3the fluorite concentrate of 1.1%.It is simple that the method has technological process, the features such as weak alkaline medium flotation, but when calcite content in raw ore is higher than fluorite, bad adaptability.
It is the flotation separation method of the carbonate fluorite ore of the inhibitor of carbonate mineral that Chinese patent (publication number: CN1032631) discloses a kind of acidified sodium silicate that adopts.The method, under common process condition, adopts one section to roughly select, four sections of selected flotation flowsheets makes carbonate and fluorite realize high-purity separation.As the 1st phase in 1985 " non-ferrous metal. ore dressing part " upper publication: " research that fluorite is separated with Calcite by Flotation ", roughly select operation and continue to use sodium carbonate, waterglass, oleic acid flotation, add acidified sodium silicate time selected and carry out commerical test, Fluorite recovery rate 79.14%, CaF
2grade 97.62%, but unreasonable due to regime of agent, fail to reach primes standard.Test shows, in fact the method is for silicate (quartz) the type fluorite ore bad adaptability of the comparatively complicated high carbon acid calcium of the embedding cloth relations of mineral such as Suichang of Zhejiang Province adit level ground, can not obtain qualified fluorite concentrate product.
In addition, flotation tailing is secondary resource, because the mining tailing utilization rate of secondary resource is low, directly causes the bulk deposition of mine tailing.Current China mill tailings volume of cargo in storage has reached more than 50 hundred million t, and annual with the speed increment of 2-3 hundred million t, brings very large difficulty to the maintenance of ecological environment.This secondary resource of mine tailing is fully utilized again, produces economic benefit, tackling key problem research must be carried out pointedly, develop the practical new technology being suitable for certain mine tailing character, reduce the cost of spoil reclaming and reprocessing, improve value-added content of product.
For complicated fluorite mineral and the flotation tailing containing fluorite, also do not have comparatively effective method can be separated fluorite and other mineral efficiently at present.
Summary of the invention
The present invention will solve the shortcoming of above-mentioned prior art, there is provided a kind of can separate complex fluorite mineral and the fluorite flotation method of flotation tailing containing fluorite effectively, have employed in this method for floating can effectively decontamination inhibitor and can the collecting agent of effective fluorite sorting, can effectively improve fluorite concentrate quality in pole.
The present invention solves the technical scheme that its technical problem adopts: the method for floating of this fluorite ore, it is characterized in that: choose raw ore, the ore accounting for raw ore total amount 56.06% ~ 70% is milled to fineness for-200 orders, breeze after mill mixes with the raw ore do not ground, add water and make the ore pulp of 20% ~ 50% concentration, under the environmental condition of 20 DEG C ~ 35 DEG C, adjusting agent is added in ore pulp, stir, ore pulp environment pH is made to be in 6.5 ~ 8.5, inhibitor is added again in ore pulp, collecting agent, stir, flotation is carried out by floator, be separated fluorite and impurity, obtain fluorite concentrate product, the adjusting agent wherein adopted is sodium carbonate, the inhibitor adopted is the medicament that waterglass and sodium fluoride combine, and the weight part ratio of waterglass and sodium fluoride is 4:1, the collecting agent adopted is the medicament of aliphatic acid and dimethyl formamide compound, and the weight part ratio of aliphatic acid and dimethyl formamide is 4:1.5.
Further, flotation comprise at least carry out one roughing, selected, scan when roughly selecting, waterglass consumption is 400 ~ 2000g/t, and sodium fluoride consumption is 100 ~ 800g/t; Time selected, waterglass consumption is 80 ~ 500g/t, and sodium fluoride consumption is 20 ~ 100g/t.
Further, when roughly selecting, the consumption of collecting agent is 100 ~ 800 g/t.
Further, the aliphatic acid in collecting agent comprises oleic acid or linoleic acid or cocinic acid or acorn nut oleic acid.
Further, by through one roughing, selected after 40% ~ 80% regrinding of products obtained therefrom to fineness-400 order, mix the product after the product of non-regrinding and regrinding, add 100 ~ 500g/t mixed inhibitor, it is selected to carry out second time.
Further, second time selected chats product selected through first time returns the section of roughly selecting with scanning together with froth pulp; Return after chats product that is selected through third time, the 4th selected gained merges and regrind; 5th time selected, the 6th chats product that is selected, the 7th selected gained returns selected successively.
Further, selected through first time, second time is selected, third time is selected, the 4th selected, the 5th selected, the 6th chats product that is selected, the 7th selected gained return successively selected or concentrated return selected.
Add sign before order number and then represent the mesh that can leak through this order number; Negative number representation can leak through the mesh of this order number, and namely particle size is less than mesh size; And positive number represents the mesh that can not leak through this order number, namely particle size is greater than mesh size.
In this method for floating, sodium fluoride can improve the selective of fluorite with the interpolation in selected operation roughly selecting, the effect that collecting agent adopts the composite drug of aliphatic acid and dimethyl formamide can strengthen collecting agent to adsorb at fluorite surface, not only effective to calcite type fluorite ore, and also effective to the sorting of fluorite in low-grade and fluorite mine tailing.The present invention is a kind of effective method for floating to complicated fluorite sorting mineral.
In floatation process, inhibitor waterglass and sodium fluoride can separately add, and also can mix interpolation; Collecting agent need be prepared before flotation.
The effect that the present invention is useful is: in method for floating of the present invention with one section roughly select add scan, flotation flowsheet that seven sections selected, and coordinate and adopt the inhibitor combined with waterglass and sodium fluoride and the collecting agent be composited with aliphatic acid and dimethyl formamide, fluorite and other mineral in the mineral such as flotation tailing that effectively can be separated common fluorite ore, complicated fluorite mineral during flotation and contain fluorite.This method for floating flotation gained concentrate good product quality, Fluorite recovery rate is good; And strong adaptability, applied range, not only can be applied to fluorite-quartz type raw ore and mineral floating mine tailing, also goes for the FLOTATION SEPARATION of fluorite in fluorite-calcite ore and low-grade fluorite ore deposit or other kind mineral.
Detailed description of the invention
The present invention is further illustrated by the following example, but not by the restriction of these embodiments.
embodiment 1:
Select Longquan, Zhejiang Province fluorite mine tailing as raw ore of the present invention, its sample ore multielement chemical composition analysis is in table 1.
the chemical composition (%) of table 1 ore
| Component | Ca | CaF 2 | CaO | BaO | MgO | SiO 2 | Al 2O 3 | K 2O | Na 2O |
| Content | 20.27 | 30.12 | 2.38 | 0.26 | 0.18 | 49.50 | 3.47 | 1.64 | 0.076 |
| Component | TFe | FeO | Fe 2O 3 | MnO | S | P | C | F | Ig |
| Content | 1.27 | 0.30 | 2.38 | 0.07 | 0.08 | 0.028 | 0.14 | 17.69 | 5.96 |
The technique that the present invention specifically processes is: be milled to ore deposit and be less than 200 orders and account for 60%, pulp density 30%, adds 1400g/t sodium carbonate adjustment pH values of pulp=8.5, adds waterglass, roughly select consumption 400g/t, stir 3 minutes; Add composite collector (oleic acid: dimethyl formamide=4:1.5) 400g/t, stir 3 minutes, flotation 6 minutes under normal temperature (20 ~ 35 DEG C) condition; Froth pulp is selected through primary blank, and the selected froth pulp of gained is regrinded to being less than 400 orders and accounted for 41%; 200 g/t waterglass are added from second time is selected, for the first time, second time gained chats product with scan froth pulp and (when scanning operation, add composite collector 100g/t, stir 3 minutes, flotation 3 minutes under normal temperature (20 ~ 35 DEG C) condition) merge after return together and roughly select; For the third time, the 4th selected gained chats returns after merging and regrinds; Five, six, seven selected chats return last operation successively; The process that all sorts all adopts common flotation device, finally obtains CaF
2grade is the fluorite concentrate of 97.89%, and Fluorite recovery rate is 95.13%.
embodiment 2:
The adit level ground fluorite ore selecting Suichang of Zhejiang Province to exploit is as raw ore of the present invention, and its raw ore multielement chemical composition analysis is in table 2, and in this ore, CaO content is higher, reaches 4.39%, belongs to the fluorite ore of high carbon acid calcium.The present invention and conventional collecting agent oleic acid are done contrast test.
the chemical composition (%) of table 2 ore
| Component | Ca | CaF 2 | CaO | BaO | MgO | SiO 2 | Al 2O 3 | K 2O | Na 2O |
| Content | 22.17 | 37.12 | 4.39 | 0.16 | 0.47 | 44.32 | 3.26 | 1.28 | 0.190 |
| Component | TFe | FeO | Fe 2O 3 | MnO | S | P | C | F | Ig |
| Content | 0.85 | 0.06 | 1.15 | 0.16 | 0.02 | 0.011 | 0.68 | 18.08 | 6.80 |
The technique that the present invention specifically processes is: be milled to ore deposit and be less than 200 orders and account for 70%, pulp density 30%, add 500g/t sodium carbonate adjustment pH values of pulp=7.5, adjust agent to add composite restrainer (waterglass: sodium fluoride=4:1), roughly select consumption 1000g/t, stir 3 minutes; Add composite collector (oleic acid: dimethyl formamide=4:1.5) 250g/t, stir 3 minutes, flotation 6 minutes under normal temperature (20 ~ 35 DEG C) condition; Froth pulp is selected through primary blank, and the selected froth pulp of gained is regrinded to being less than 400 orders and accounted for 60%; Waterglass 300 g/t is added from second time is selected, for the first time, second time gained chats product with scan froth pulp and (scan operation and add composite collector 100g/t, stir 3 minutes, flotation 3 minutes under normal temperature (20 ~ 35 DEG C) condition) merge after return together and roughly select; For the third time, the 4th selected gained chats returns after merging and regrinds; Five, six, seven selected chats return last operation successively; The process that all sorts all adopts common flotation device, finally obtains CaF
2grade is the fluorite concentrate of 97.81%, and Fluorite recovery rate is 79.96%.Other technological operations are constant, change composite collector into oleic acid, only can obtain CaF
2the concentrate product of grade 90.38%.
embodiment 3:
Select Wuyi In Zhejiang flotation tailing (containing 29.06% CaF
2, main valuable mineral is fluorite, and gangue mineral based on quartz, and has calcite and a small amount of sericite, irony thing, the sulfide-pyrite of trace), because there is no successful floatation process process, be forced to store up for a long time.Be milled to ore deposit and be less than 200 orders and account for 56.06%, pulp density 30%, add 1000g/t sodium carbonate adjustment pH values of pulp=7.5, adjust agent, roughly selects consumption 1000g/t to add composition (waterglass: sodium fluoride=4:1), stirs 3 minutes; Add composite collector (oleic acid: dimethyl formamide=4:1.5) 400g/t, stir 3 minutes, flotation 6 minutes under normal temperature (20 ~ 35 DEG C) condition; Gained froth pulp is regrinded to being less than 400 orders and is accounted for 76.18%; First time selectedly adds composite restrainer 800 g/t, and selected beginning of second time adds composite restrainer 400 g/t, and selected chats returns last operation successively; The process that all sorts all adopts common flotation device, finally obtains CaF
2grade is the fluorite concentrate of 98.40%, and Fluorite recovery rate is 93.24%.
embodiment 4:
Select the raw ore that is produced from Qingtian County of Zhejiang, the ore accounting for raw ore total amount 56.06% is milled to fineness for-200 orders, breeze after mill mixes with the raw ore do not ground, and adds water and makes the ore pulp of 20% concentration, under the environmental condition of 20 DEG C ~ 35 DEG C, adjusting agent is added in ore pulp, stir, make ore pulp environment pH be in 6.5, then add inhibitor, collecting agent in ore pulp, stir, by floator at least carry out one roughing, selected, scan.By through one roughing, selected after 40% regrinding of products obtained therefrom to fineness-400 order, mix the product after the product of non-regrinding and regrinding, add 100g/t mixed inhibitor, it is selected to carry out second time., second time selected chats product selected through first time returns the section of roughly selecting with scanning together with froth pulp; Return after chats product that is selected through third time, the 4th selected gained merges and regrind; 5th time selected, the 6th chats product that is selected, the 7th selected gained returns selected successively.Be separated fluorite and impurity, obtain fluorite concentrate product.The adjusting agent wherein adopted is sodium carbonate; The inhibitor adopted is the medicament that waterglass and sodium fluoride combine, and the weight part ratio of waterglass and sodium fluoride is 4:1; The collecting agent adopted is the medicament of aliphatic acid and dimethyl formamide compound, and the weight part ratio of aliphatic acid and dimethyl formamide is 4:1.5.When roughly selecting, waterglass consumption is 400g/t, and sodium fluoride consumption is 100g/t; Time selected, waterglass consumption is 80g/t, and sodium fluoride consumption is 20g/t.The consumption of collecting agent is 100g/t.Aliphatic acid in collecting agent is linoleic acid.Obtain fluorite concentrate grade 94.62%, the rate of recovery 82.53%.
embodiment 5:
Select the raw ore that Zhejiang Jiaxing is produced, the ore accounting for raw ore total amount 70% is milled to fineness for-200 orders, breeze after mill mixes with the raw ore do not ground, and adds water and makes the ore pulp of 50% concentration, under the environmental condition of 35 DEG C, adjusting agent is added in ore pulp, stir, make ore pulp environment pH be in 8.5, then add inhibitor, collecting agent in ore pulp, stir, by floator at least carry out one roughing, selected, scan.By through one roughing, selected after 80% regrinding of products obtained therefrom to fineness-400 order, mix the product after the product of non-regrinding and regrinding, add 500g/t mixed inhibitor, it is selected to carry out second time.Selected through first time, second time is selected, third time is selected, the 4th selected, the 5th selected, the 6th chats product that is selected, the 7th selected gained return successively selected or concentrated return selected.The adjusting agent wherein adopted is sodium carbonate; The inhibitor adopted is the medicament that waterglass and sodium fluoride combine, and the weight part ratio of waterglass and sodium fluoride is 4:1; The collecting agent adopted is the medicament of aliphatic acid and dimethyl formamide compound, and the weight part ratio of aliphatic acid and dimethyl formamide is 4:1.5.When roughly selecting, waterglass consumption is 2000g/t, and sodium fluoride consumption is 800g/t; Time selected, waterglass consumption is 500g/t, and sodium fluoride consumption is 100g/t.The consumption of collecting agent is 800 g/t.Aliphatic acid in collecting agent is cocinic acid.Obtain fluorite concentrate grade 97.04%, the rate of recovery 90.13%.
embodiment 6:
Select the raw ore that Zhejiang dragon trip is produced, the ore accounting for raw ore total amount 63.03% is milled to fineness for-200 orders, breeze after mill mixes with the raw ore do not ground, and adds water and makes the ore pulp of 35% concentration, under the environmental condition of 20 DEG C ~ 35 DEG C, adjusting agent is added in ore pulp, stir, make ore pulp environment pH be in 7.5, then add inhibitor, collecting agent in ore pulp, stir, by floator at least carry out one roughing, selected, scan.By through one roughing, selected after 60% regrinding of products obtained therefrom to fineness-400 order, mix the product after the product of non-regrinding and regrinding, add 300g/t mixed inhibitor, it is selected to carry out second time., second time selected chats product selected through first time returns the section of roughly selecting with scanning together with froth pulp; Return after chats product that is selected through third time, the 4th selected gained merges and regrind; 5th time selected, the 6th chats product that is selected, the 7th selected gained returns selected successively.The adjusting agent wherein adopted is sodium carbonate; The inhibitor adopted is the medicament that waterglass and sodium fluoride combine, and the weight part ratio of waterglass and sodium fluoride is 4:1; The collecting agent adopted is the medicament of aliphatic acid and dimethyl formamide compound, and the weight part ratio of aliphatic acid and dimethyl formamide is 4:1.5.When roughly selecting, waterglass consumption is 1200g/t, and sodium fluoride consumption is 450g/t; Time selected, waterglass consumption is 290g/t, and sodium fluoride consumption is 60g/t.The consumption of collecting agent is 450g/t.Aliphatic acid in collecting agent is acorn nut oleic acid.Obtain fluorite concentrate grade 95.47%, the rate of recovery 89.93%.
embodiment 7:
Select Hunan Ningxiang low-grade fluorite ore deposit (containing 38.29% CaF
2), be milled to and be less than 200 orders and account for 65%; Add 1000g/t sodium carbonate adjustment pH values of pulp=7.5, with composition (waterglass: sodium fluoride=4:1), adjust agent, roughly selects consumption 1000 g/t, and selected consumption 300 g/t, method is with example 1.Obtain fluorite concentrate grade 98.31%, the rate of recovery 83.49%.
embodiment 8:
Select Chifeng fluorite-barite deposit, containing 48.29%CaF
2, 27.26%BaSO
4, adopt conventional flotation technology can only obtain fluorite-barite bulk concentrate product, with composite restrainer (waterglass: sodium fluoride: hydrochloric acid=4:1:0.5), adjust agent, roughly selects consumption 950 g/t, and selected consumption 500 g/t, method is with example 1.Obtain fluorite concentrate grade 98.07%, the rate of recovery 87.49%.
Above embodiment can be found out, the present invention is by the application of composite restrainer and composite collector and this floatation process method, effectively can make the minerals separation such as fluorite and quartz, fluorite and calcite, achieve the sorting of the complicated mineral such as high carbon acid salt form fluorite ore, low-grade fluorite ore deposit and flotation tailing.
Although the present invention has illustrated by reference to preferred embodiment and has described, those skilled in the art should understand, and in the scope of claims, can do the various change in form and details.
Claims (6)
1. the method for floating of a fluorite ore, it is characterized in that: choose raw ore, the ore accounting for raw ore total amount 56.06% ~ 70% is milled to fineness for-200 orders, breeze after mill mixes with the raw ore do not ground, add water and make the ore pulp of 20% ~ 50% concentration, under the environmental condition of 20 DEG C ~ 35 DEG C, adjusting agent is added in ore pulp, stir, make ore pulp environment pH be in 6.5 ~ 8.5, then add inhibitor, collecting agent in ore pulp, stir, carry out flotation by floator, be separated fluorite and impurity, obtain fluorite concentrate product; The adjusting agent wherein adopted is sodium carbonate; The inhibitor adopted is the medicament that waterglass and sodium fluoride combine, and the weight part ratio of waterglass and sodium fluoride is 4:1; The collecting agent adopted is the medicament of aliphatic acid and dimethyl formamide compound, and the weight part ratio of aliphatic acid and dimethyl formamide is 4:1.5.
2. the method for floating of fluorite ore according to claim 1, is characterized in that: the consumption of collecting agent is 100 ~ 800 g/t.
3. the method for floating of fluorite ore according to claim 1, is characterized in that: the aliphatic acid in described collecting agent comprises oleic acid or linoleic acid or cocinic acid or acorn nut oleic acid.
4. the method for floating of the fluorite ore according to Claims 2 or 3, it is characterized in that: by through one roughing, selected after 40% ~ 80% regrinding of products obtained therefrom to fineness-400 order, mix the product after the product of non-regrinding and regrinding, add 100 ~ 500g/t mixed inhibitor, it is selected to carry out second time.
5. the method for floating of fluorite ore according to claim 4, is characterized in that:, second time selected chats product selected through first time returns the section of roughly selecting with scanning together with froth pulp; Return after chats product that is selected through third time, the 4th selected gained merges and regrind; 5th time selected, the 6th chats product that is selected, the 7th selected gained returns selected successively.
6. the method for floating of fluorite ore according to claim 4, is characterized in that: selected through first time, second time is selected, third time is selected, the 4th selected, the 5th selected, the 6th chats product that is selected, the 7th selected gained return successively selected or concentrated return selected.
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| CN112517233A (en) * | 2020-12-21 | 2021-03-19 | 龙泉市砩矿有限责任公司 | Fluorite processing production line and processing technology thereof |
| CN113369021A (en) * | 2021-05-10 | 2021-09-10 | 中南大学 | Fluorite anion-nonionic association body collecting agent, preparation method and application method thereof |
| CN114804179A (en) * | 2022-06-02 | 2022-07-29 | 中南大学 | Method for recovering high-purity calcium fluoride from fluorine-containing waste residues |
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| CN1015601B (en) * | 1987-07-22 | 1992-02-26 | 广州有色金属研究院 | Floatation of fluor spar |
| CN1032631A (en) * | 1988-09-17 | 1989-05-03 | 郑州轻金属研究所 | Carbonate-fluorite flotation separation method |
| RU2268089C1 (en) * | 2004-08-17 | 2006-01-20 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский, проектный и конструкторский институт горного дела и металлургии цветных металлов" ФГУП "Гипроцветмет" | Process of flotation concentration of fluorite ores |
| CN102091673B (en) * | 2009-12-11 | 2012-12-12 | 山东招金集团有限公司 | Low-grade fluorite silicon reduction mineral processing process |
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