阅读说明：本技术 含钨钼低品位伴生萤石矿浮选方法 (Flotation method for low-grade associated fluorite ore containing tungsten and molybdenum ) 是由 纪道河 李英标 杨勇祥 蒋传辉 李志雄 龙会友 胡岳华 孙伟 韩海生 亢建华 王 于 2021-08-25 设计创作，主要内容包括：本发明公开了一种含钨钼低品位伴生萤石矿浮选方法包括如下步骤：(1)原矿经破碎、磨矿、磁选、浮选得到钨钼浮选尾矿；(2)钨钼浮选尾矿采用碳酸钠和氢氧化钠作为pH调整剂、水玻璃和聚羧酸为抑制剂、混合脂肪酸为捕收剂进行粗选作业,得到萤石粗选精矿和粗选尾矿；(3)萤石粗选尾矿中加入混合脂肪酸进行一次粗扫选,得到粗扫选精矿和粗扫选尾矿；(4)萤石粗选精矿依次进行精选,精选一和精选二采用酸化水玻璃为抑制剂,中矿合并后进行精扫选,得到精扫选精矿和精扫选尾矿；(5)萤石精选三采用酸化水玻璃为抑制剂,精选四、精选五和精选六采用有机膦酸为抑制剂,得到萤石精矿。本发明能够高效回收萤石。(The invention discloses a flotation method of tungsten-molybdenum-containing low-grade associated fluorite ore, which comprises the following steps: (1) crushing, grinding, magnetically separating and floating raw ores to obtain tungsten-molybdenum flotation tailings; (2) carrying out roughing operation on the tungsten-molybdenum flotation tailings by adopting sodium carbonate and sodium hydroxide as pH regulators, water glass and polycarboxylic acid as inhibitors and mixed fatty acid as collectors to obtain fluorite roughed concentrate and roughed tailings; (3) adding mixed fatty acid into the fluorite roughing tailings to perform primary roughing to obtain roughing concentrate and roughing tailings; (4) selecting the fluorite rough concentration concentrate in sequence, wherein acidified water glass is adopted as an inhibitor in the first selection and the second selection, and fine scavenging is carried out after middlings are combined to obtain fine scavenging concentrate and fine scavenging tailings; (5) and adopting acidified water glass as an inhibitor for the third fluorite concentration, and adopting organic phosphonic acid as an inhibitor for the fourth fluorite concentration, the fifth fluorite concentration and the sixth fluorite concentration to obtain fluorite concentrate. The invention can efficiently recover fluorite.)

1. A flotation method of low-grade associated fluorite ore containing tungsten and molybdenum is characterized by comprising the following steps:

(1) crushing, grinding, magnetically separating and floating raw ore to recover valuable metals such as iron, molybdenum, bismuth, tungsten and the like to obtain tungsten-molybdenum flotation tailings;

(2) roughing, wherein mixed alkali of sodium carbonate and sodium hydroxide is used as a pH regulator, water glass and polycarboxylic acid are used as inhibitors, and mixed fatty acid is used as a collecting agent for roughing of the tungsten-molybdenum flotation tailings, so that fluorite roughing concentrate and roughing tailings are obtained;

(3) performing rough scavenging, namely adding mixed fatty acid into the fluorite rough tailings for primary rough scavenging to obtain rough scavenging concentrate and rough scavenging tailings, wherein the rough scavenging concentrate returns to the rough scavenging operation, and the rough scavenging tailings are directly discharged;

(4) performing secondary concentration and fine scavenging, wherein the fluorite roughing concentrate is sequentially subjected to concentration, a first concentration step and a second concentration step adopt acidified water glass as an inhibitor, middlings of the first concentration step and the second concentration step are combined and then subjected to fine scavenging to obtain fine scavenging concentrate and fine scavenging tailings, wherein the fine scavenging concentrate returns to the first concentration step, and the fine scavenging tailings are directly discharged;

(5) selecting for four times, wherein the third fluorite selection adopts acidified water glass as an inhibitor, the fourth selection, the fifth selection and the sixth selection adopt organic phosphonic acid as an inhibitor, and middlings in the selection are returned in sequence to finally obtain the grade of CaF₂Grade not less than 85% CaCO₃Fluorite concentrate less than or equal to 10 percent.

2. The method of claim 1, further comprising: in the step (1), the concentration of the tungsten-molybdenum flotation tailings is 25-30%, the fineness of-0.074 mm accounts for 75-80%, and the content of CaF₂Grade of 10-15% CaCO₃The grade is 4-10%.

3. The method of claim 1, further comprising: in the step (2), the pH regulator is mixed alkali of sodium carbonate and sodium hydroxide, the concentration is 5-10%, the weight ratio of the sodium carbonate to the sodium hydroxide is 9:1, and the pH of fluorite roughing is 10-10.5; the dosage of the water glass is 800-1000g/t, and the dosage of the polycarboxylic acid is 100-150 g/t; the mixed fatty acid is modified oleic acid and oxidized paraffin soap, the concentration is 5-10%, the mixing weight ratio of the modified oleic acid to the oxidized paraffin soap is 1-3:1-3, and the dosage is 400 g/t.

4. The method of claim 1, further comprising: in the step (3), the pH value of the fluorite rough scavenging is 10-10.5, and the dosage of the mixed fatty acid is 50-80 g/t.

5. The method of claim 1, further comprising: in the step (4), the acidified water glass is prepared from sulfuric acid and water glass, the weight ratio is 1:1-3, and the concentration is 5-10%; the dosage of the selected first acidified water glass is 300-400g/t, and the dosage of the selected second acidified water glass is 200-300 g/t.

6. The method of claim 1, further comprising: in the step (5), the dosage of the acidified water glass is 100-200 g/t; the concentration of the organic phosphonic acid is 1-2%, and the dosage of the fourth concentration, the fifth concentration and the sixth concentration is 50g/t, 30g/t and 20g/t respectively.

7. The method of claim 1, further comprising: the first operation of the fluorite roughing and the fine selection adopts a flotation column, and the scavenging and other fine selection operations adopt a flotation machine.

8. The method of claim 3, further comprising: the mixing weight ratio of the modified oleic acid to the oxidized paraffin soap is 3:2 or 1:1 or 2: 3.

9. The method of claim 5, further comprising: the mixing weight ratio of the sulfuric acid to the water glass is 1:1 or 1:2 or 1: 3.

10. The method of claim 1, further comprising: the raw ore is associated ore of multi-metal of iron, molybdenum, bismuth, sulfur, tungsten and fluorite, and the grade of the fluorite is 10-15%.

Technical Field

The invention relates to a beneficiation method, in particular to a flotation method of low-grade associated fluorite ore containing tungsten and molybdenum.

Background

Fluorite is the most important raw material in the field of fluorine chemical industry, is a typical non-renewable non-metallic mineral resource, and has very wide application in the traditional industries such as metallurgy, building materials, ceramics, glass, hydrofluoric acid and the like and the emerging industries such as new energy, national defense, electronics, medicine and the like, so the fluorine chemical industry is called as the gold industry.

China is the largest fluorite producing country in the world, but the single type high-quality fluorite reserves are few, the multi-metal complex associated fluorite reserves are large, and the fluorite reserves are mainly distributed in inner Mongolia, Zhejiang, Fujian, Jiangxi, Hunan and other provinces. Meanwhile, China is also the largest fluorite consumer country in the world. With the increasing exhaustion of single fluorite resource, the efficient development and utilization of complex associated fluorite resource, such as the efficient utilization of tungsten molybdenum tailings low-grade associated fluorite resource, has important significance for guaranteeing the supply of fluorite products, relieving the fluorite demand and promoting the healthy and sustainable development of fluorite industry in China, and is an important direction for developing and utilizing the fluorite resource in the future.

Due to the associated low-grade associated fluorite of tungsten-molybdenum tailings, nonferrous metals such as tungsten-molybdenum and the like and rare metals, the mineral co-associated embedding relationship is complex, the gangue minerals are various, the fluorite is difficult to be efficiently enriched, the oleic acid anion collecting agent has poor selectivity, weak adaptability and insufficient low-temperature resistance, and the influence of factors such as calcium-containing gangue minerals, temperature, water quality, impurity ions and the like on fluorite flotation is difficult to overcome, so that the associated fluorite recovery efficiency is low and the resource waste is serious. Therefore, the development of a clean and efficient flotation process for improving the comprehensive utilization rate of the low-grade associated fluorite resource of the tungsten-molybdenum tailings is a technical problem which needs to be solved urgently in the field.

Disclosure of Invention

The invention aims to provide a clean and efficient flotation method for tungsten-molybdenum-containing low-grade associated fluorite ore.

In order to solve the technical problem, the flotation method of the low-grade associated fluorite ore containing tungsten and molybdenum comprises the following steps:

(1) crushing, grinding, magnetically separating and floating raw ore to recover valuable metals such as iron, molybdenum, bismuth, tungsten and the like to obtain tungsten-molybdenum flotation tailings;

(2) roughing, wherein mixed alkali of sodium carbonate and sodium hydroxide is used as a pH regulator, water glass and polycarboxylic acid are used as inhibitors, and mixed fatty acid is used as a collecting agent for roughing of the tungsten-molybdenum flotation tailings, so that fluorite roughing concentrate and roughing tailings are obtained;

(3) performing rough scavenging, namely adding mixed fatty acid into the fluorite rough tailings for primary rough scavenging to obtain rough scavenging concentrate and rough scavenging tailings, wherein the rough scavenging concentrate returns to the rough scavenging operation, and the rough scavenging tailings are directly discharged;

(4) performing secondary concentration and fine scavenging, wherein the fluorite roughing concentrate is sequentially subjected to concentration, a first concentration step and a second concentration step adopt acidified water glass as an inhibitor, middlings of the first concentration step and the second concentration step are combined and then subjected to fine scavenging to obtain fine scavenging concentrate and fine scavenging tailings, wherein the fine scavenging concentrate returns to the first concentration step, and the fine scavenging tailings are directly discharged;

(5) selecting for four times, wherein the third fluorite selection adopts acidified water glass as an inhibitor, the fourth selection, the fifth selection and the sixth selection adopt organic phosphonic acid as an inhibitor, and middlings in the selection are returned in sequence to finally obtain the grade of CaF₂Grade not less than 85% CaCO₃Fluorite concentrate less than or equal to 10 percent.

In the step (1), the concentration of the tungsten-molybdenum flotation tailings is 25-30%, the fineness of-0.074 mm accounts for 75-80%, and the content of CaF₂Grade of 10-15% CaCO₃The grade is 4-10%.

In the step (2), the pH regulator is mixed alkali of sodium carbonate and sodium hydroxide, the concentration is 5-10%, the weight ratio of the sodium carbonate to the sodium hydroxide is 9:1, and the pH of fluorite roughing is 10-10.5; the dosage of the water glass is 800-1000g/t, and the dosage of the polycarboxylic acid is 100-150 g/t; the mixed fatty acid is modified oleic acid and oxidized paraffin soap, the concentration is 5-10%, the mixing weight ratio of the modified oleic acid to the oxidized paraffin soap is 1-3:1-3, and the dosage is 400 g/t.

In the step (3), the pH value of the fluorite rough scavenging is 10-10.5, and the dosage of the mixed fatty acid is 50-80 g/t.

In the step (4), the acidified water glass is prepared from sulfuric acid and water glass, the weight ratio is 1:1-3, and the concentration is 5-10%; the dosage of the selected first acidified water glass is 300-400g/t, and the dosage of the selected second acidified water glass is 200-300 g/t.

In the step (5), the dosage of the acidified water glass is 100-200 g/t; the concentration of the organic phosphonic acid is 1-2%, and the dosage of the fourth concentration, the fifth concentration and the sixth concentration is 50g/t, 30g/t and 20g/t respectively.

The first operation of the fluorite roughing and the fine selection adopts a flotation column, and the scavenging and other fine selection operations adopt a flotation machine.

The mixing weight ratio of the modified oleic acid to the oxidized paraffin soap is 3:2 or 1:1 or 2: 3.

The mixing weight ratio of the sulfuric acid to the water glass is 1:1 or 1:2 or 1: 3.

The raw ore is associated ore of multi-metal of iron, molybdenum, bismuth, sulfur, tungsten and fluorite, and the grade of the fluorite is 10-15%.

Aiming at the difficulty of the associated fluorite recovery technology, the method adopts the steps of rough concentration, rough scavenging, secondary concentration, fine scavenging and four times of concentration to be tightly combined, correspondingly develops the mixed fatty acid high-selectivity fluorite collecting agent, realizes the coordination and optimization of the selectivity and the collecting capacity, adopts polycarboxylic acid and organic phosphoric acid organic inhibitor, strengthens the step-by-step inhibition of calcium-containing gangue minerals such as calcite and the like, adopts the flotation process of partial open circuit in the concentration stage, reduces the influence of the calcite on the fluorite enrichment efficiency, promotes the high-efficiency separation of the fluorite and the calcite, realizes the high-efficiency recovery and utilization of low-grade associated fluorite, and the grade of the obtained fluorite concentrate can reach more than 85 percent and the recovery rate can reach more than 55 percent.

The flotation method of the tungsten-molybdenum-containing low-grade associated fluorite ore has the following technical innovation and characteristics:

(1) according to the invention, mixed fatty acid of oleic acid and oxidized paraffin soap is used as fluorite collecting agent, and the optimized proportion of modified oleic acid and oxidized paraffin soap is 3:2, 1:1 or 2:3 through repeated tests, so that the coordination and optimization of the selectivity and the collecting capacity are realized, and the selective collection of fluorite is enhanced;

(2) the mixed alkali of sodium carbonate and sodium hydroxide is used as the pH regulator, so that the consumption of soda ash is effectively reduced, and the cost of beneficiation reagent is reduced;

(3) according to the method, polycarboxylic acid and organic phosphonic acid inhibitors are adopted in the method test, and the calcium-containing gangue minerals such as fluorite, calcite and the like are effectively separated by a method of coarse selection and fine selection for step-by-step inhibition;

(4) the method adopts the steps of rough concentration, rough scavenging, secondary concentration, fine scavenging and concentration for four times, and develops the flotation reagents correspondingly, and the flotation reagents are matched with each other, so that the defects of the prior art are overcome, the aim of the invention is fulfilled, and the low-grade associated fluorite is recycled efficiently;

(5) the method has simple process flow, reduces the using amount of the water glass, lightens the pressure of standard discharge of the wastewater, and improves the utilization rate of the associated fluorite.

Detailed Description

The present invention will be described in detail with reference to specific embodiments below:

the flotation method of the low-grade associated fluorite ore containing tungsten and molybdenum comprises the following steps:

(1) the raw ore is associated ore of multi-metal of iron, molybdenum, bismuth, sulfur, tungsten and fluorite, and the grade of the fluorite is 10-15%. The raw ore is crushed, ground, magnetically separated, floated and recycled to obtain the tungsten-molybdenum flotation tailings. The concentration of the tungsten-molybdenum flotation tailings is 25-30%, the fineness of-0.074 mm accounts for 75-80%, and the content of CaF₂Grade of 10-15% CaCO₃The grade is 4-10%.

(2) And (3) roughing, wherein mixed alkali of sodium carbonate and sodium hydroxide is used as a pH regulator, water glass and polycarboxylic acid are used as inhibitors, and mixed fatty acid is used as a collecting agent for roughing the tungsten-molybdenum flotation tailings, so that fluorite roughing concentrate and roughing tailings are obtained. The pH regulator is mixed alkali of sodium carbonate and sodium hydroxide, the concentration is 5-10%, the weight ratio of the sodium carbonate to the sodium hydroxide is 9:1, and the crude selection pH of fluorite is 10-10.5. The dosage of the water glass is 800-1000g/t, and the dosage of the polycarboxylic acid is 100-150 g/t. The mixed fatty acid is modified oleic acid and oxidized paraffin soap, the concentration is 5-10%, the mixing weight ratio of the modified oleic acid to the oxidized paraffin soap is 1-3:1-3, more preferably 3:2, 1:1 or 2:3, and the dosage is 300-400 g/t.

(3) And (3) rough scavenging, namely adding mixed fatty acid into the fluorite rough tailings for primary rough scavenging to obtain rough scavenging concentrate and rough scavenging tailings, wherein the rough scavenging concentrate returns to the rough scavenging operation, and the rough scavenging tailings are directly discharged. The pH value of the fluorite rough scavenging is 10-10.5, and the dosage of the mixed fatty acid is 50-80 g/t.

(4) And (2) secondary concentration and fine scavenging, wherein the fluorite rough concentration concentrate is sequentially subjected to concentration, first concentration and second concentration adopt acidified water glass as an inhibitor, middlings of the first concentration and the second concentration are combined and then subjected to fine scavenging to obtain fine scavenging concentrate and fine scavenging tailings, the fine scavenging concentrate returns to the first concentration, and the fine scavenging tailings are directly discharged. The acidified water glass is prepared from sulfuric acid and water glass in a weight ratio of 1:1-3, preferably 1:1, 1:2 or 1:3, and has a concentration of 5-10%; the dosage of the selected first acidified water glass is 300-400g/t, and the dosage of the selected second acidified water glass is 200-300 g/t.

(5) Selecting for four times, wherein the third fluorite selection adopts acidified water glass as an inhibitor, the fourth selection, the fifth selection and the sixth selection adopt organic phosphonic acid as an inhibitor, and middlings in the selection are returned in sequence to finally obtain the grade of CaF₂Grade not less than 85% CaCO₃Fluorite concentrate less than or equal to 10 percent. The dosage of the acidified water glass is 100-200 g/t. The concentration of the organic phosphonic acid is 1-2%, and the dosage of the fourth concentration, the fifth concentration and the sixth concentration are respectively 50g/t, 30g/t and 20g/t

The first operation of rough concentration and fine concentration of fluorite adopts a flotation column, and the second operation of scavenging and other fine concentration adopts a flotation machine.

Example one

The major valuable minerals in Chenzhou of Hunan province are magnetite, molybdenite, bismuth ore, scheelite, fluorite and the like, the major gangue minerals are garnet, calcite, feldspar, quartz and the like, the contents of iron, molybdenum, bismuth, tungsten and fluorite are respectively 9.8%, 0.14%, 0.02%, 0.23% and 12.91%, and the content of calcite is 6.46%. After crushing, grinding, magnetic separation and flotation of raw ore to recover valuable metals such as iron, molybdenum, bismuth, tungsten and the like, comprehensive recovery of fluorite is carried out, and fluorite concentrate with the grade of more than 85% is finally obtained.

(1) The modified oleic acid and the oxidized paraffin soap are prepared into a mixed fatty acid collecting agent with the concentration of 10% according to the proportion of 3:2, and concentrated sulfuric acid and water glass are prepared into acidified water glass with the concentration of 5% according to the proportion of 1: 1. Adding mixed alkali, water glass, polycarboxylic acid and mixed fatty acid into the tungsten molybdenum tailings with the concentration of 30% and the fineness of-0.074 mm accounting for 75% in sequence to carry out fluorite roughing, wherein the pH value of roughing is controlled to be 10.5, the using amount of the water glass is 1000g/t, the using amount of the polycarboxylic acid is 100g/t, and the using amount of the mixed fatty acid is 300g/t, so as to obtain roughing concentrate and roughing tailings.

(2) Adding 50g/t of mixed fatty acid into the rougher tailings to perform rough scavenging operation, returning rough scavenging concentrate to the rougher operation, and enabling the rough scavenging tailings to enter a tailing pond.

(3) Adding 300g/t and 200g/t of acidified water glass serving as an inhibitor into the first fluorite concentration step and the second fluorite concentration step respectively, combining middlings of the first fluorite concentration step and the second fluorite concentration step, then carrying out fine scavenging, returning fine scavenging concentrate to the first fluorite concentration step, and enabling fine scavenging tailings to enter a tailing pond.

(4) The third fluorite selection adopts acidified water glass as an inhibitor, and the dosage of the acidified water glass is 100g/t, and the fourth fluorite selection, the fifth fluorite selection and the sixth fluorite selection adopt organic phosphonic acid as the inhibitor, and the dosage of the organic phosphonic acid is 50g/t, 30g/t and 20g/t respectively.

(5) Through the process flow of one-time roughing, two-time scavenging and six-time concentration and partial open circuit in the concentration stage, the fluorite concentrate with the grade of more than 85% and the recovery rate of more than 55% is finally obtained.

Example two

The tungsten-molybdenum flotation tailings in Hunan province mainly contain the gangue minerals of calcium-iron garnet, calcite, feldspar, quartz and the like, and CaF₂14.82% of CaCO₃The content was 4.10%. Adjusting the pH value of the tungsten-molybdenum tailings to 10 by adopting mixed alkali of sodium carbonate and sodium hydroxide, sequentially adding water glass and polycarboxylic acid combination inhibitor, wherein the using amount of the water glass is 1000g/t, the using amount of the polycarboxylic acid is 100g/t, stirring for 3min, adding mixed fatty acid, wherein the ratio of the modified oleic acid to the oxidized paraffin soap is 1:1, the using amount of the modified oleic acid to the oxidized paraffin soap is 350g/t, and stirring for 5min, and then carrying out a flotation roughing experiment. The concentration adopts acidified water glass and organic phosphonic acid as inhibitors, and the fluorite concentrate with the grade of 96.39% and the recovery rate of 62.65% is obtained through a closed experimental process of primary coarse, primary fine, secondary fine and secondary fine open circuits, and the grade of calcite in the concentrate is 2.18%.