阅读说明：本技术 一种石英-方解石型萤石矿的正反浮选工艺 (Positive and negative flotation process for quartz-calcite type fluorite ore ) 是由 刘养春 宋文义 杨勇 刘星强 刘云涛 于 2018-07-30 设计创作，主要内容包括：本发明公开了石英-方解石型萤石矿的正反浮选工艺,通过正浮选脱除石英脉石,然后反浮选脱除方解石脉石,最终得到萤石精矿。将矿石经破碎磨矿至单体解离,加水调浆至一定浓度,流入搅拌槽,再向矿浆中分别加入调整剂碳酸钠、水玻璃和正浮选捕收剂进行调浆,调浆后的物料进入正浮选系统进行正浮选粗选,粗选泡沫经精选；精选泡沫进入反浮选搅拌槽,分别加入反浮选调整剂硫酸、柠檬酸和反浮选捕收剂进行调浆,调浆后的物料进入反浮选系统进行方解石矿物反浮选,泡沫产品经过扫选为反浮选尾矿,槽内产品为萤石精矿。本发明工艺具有分选效率高,工艺指标优,精矿易于过滤等优点。(The invention discloses a direct-reverse flotation process of quartz-calcite fluorite ore, which removes quartz gangue through direct flotation, and then removes calcite gangue through reverse flotation to finally obtain fluorite concentrate. Crushing and grinding ores until the ores are dissociated into monomers, adding water, mixing the pulp to a certain concentration, flowing into a stirring tank, respectively adding regulators of sodium carbonate, water glass and a positive flotation collecting agent into the ore pulp for size mixing, feeding the mixed material into a positive flotation system for positive flotation roughing, and finely selecting roughing foams; the selected foam enters a reverse flotation stirring tank, reverse flotation regulators such as sulfuric acid, citric acid and a reverse flotation collector are added respectively for size mixing, the mixed material enters a reverse flotation system for reverse flotation of calcite minerals, foam products are subjected to scavenging to form reverse flotation tailings, and products in the tank are fluorite concentrates. The process has the advantages of high separation efficiency, excellent process indexes, easy filtration of concentrate and the like.)

1. A direct-reverse flotation process of quartz-calcite fluorite ore is characterized in that: removing quartz gangue by direct flotation, and removing calcite gangue by reverse flotation to finally obtain fluorite concentrate.

2. The direct and reverse flotation process as claimed in claim 1, wherein the specific steps of removing quartz gangue by direct flotation are as follows: crushing and grinding quartz-calcite fluorite ore until mineral monomers are dissociated, adding water for size mixing, then flowing into a stirring tank, respectively adding a regulator, an inhibitor and a direct flotation collector into the ore pulp for size mixing, feeding the material after size mixing into a direct flotation system for direct flotation roughing, wherein products in the tank are tailings, the roughing foam products are refined for 1-10 times, and the tailings after the direct flotation are gradually returned to the previous flotation operation.

3. The direct and reverse flotation process according to claim 1, wherein the reverse flotation is performed by removing calcite gangue through the following steps: and (3) enabling the concentrated foam of the direct flotation to enter a reverse flotation stirring tank, respectively adding a reverse flotation regulator, an inhibitor and a reverse flotation collector to carry out size mixing, enabling the material after size mixing to enter a reverse flotation system to carry out reverse flotation of calcite minerals, enabling the product in the tank to be fluorite concentrate, carrying out scavenging on the foam product for 1-10 times, and enabling the scavenged concentrate of the reverse flotation to gradually return to the previous flotation operation.

4. The direct reverse flotation process according to claim 1 or 2, wherein the direct flotation collector is a fatty acid, a fatty acid soap or a combination of a fatty acid soap and a surfactant.

5. The direct and reverse flotation process according to claim 1 or 3, wherein the reverse flotation collector is an alkylamine bis-methylphosphonic acid with the formula RN (CH) ₂PO ₃H ₂) ₂R is C ₈～C ₁₈Alkyl or aryl.

6. The direct-reverse flotation process according to claim 1 or 2, wherein the pH value of the direct flotation pulp is 8-11, and the regulator is selected from sodium carbonate, sodium hydroxide, potassium hydroxide or ammonia water; the inhibitor is preferably water glass.

7. The direct reverse flotation process according to claim 1 or 3, wherein the pulp subjected to reverse flotation has a pH value of 4-6, and the adjusting agent is selected from sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid; the inhibitor is preferably citric acid.

8. The direct-reverse flotation process according to claim 1 or 2, wherein the inhibitor water glass is added in the direct flotation concentration operation in an amount of 0.1-0.8 kg/t.

9. The direct-reverse flotation process according to claim 1 or 3, wherein the reverse flotation scavenging operation comprises the addition of a regulator sulfuric acid and an inhibitor citric acid, wherein the addition amount of the sulfuric acid is 1.0-3.0 kg/t, and the addition amount of the citric acid is 0.1-0.5 kg/t.

Technical Field

The invention belongs to the technical field of fluorite ore flotation, and particularly relates to a flotation enrichment process of quartz-calcite fluorite ore.

Background

Fluorite ore is the main source of fluorine element in industry and is an important nonmetallic mineral raw material. With the rapid development of fluoropolymers and fluorine-containing fine chemicals worldwide, the position of fluorite ore as an industrial base material is more and more important and has become an important strategic material. The fluorite ore resources are rich in China, but poor ores and refractory intergrowth ores are abundant, and the impurity removal is the main purpose of fluorite ore dressing. The flotation method is the most common method for obtaining high-grade fluorite concentrate at present, and the selection of a proper flotation process is the key of fluorite impurity removal.

Fluorite ore in China mainly has three types: quartz-fluorite ore, quartz-barite-fluorite ore and quartz-calcite-fluorite ore. For quartz-fluorite ore, sodium carbonate and water glass are used as regulators, fatty acid or fatty acid soap is used as a collecting agent, and enrichment of fluorite can be easily realized through rough concentration and multiple fine concentration. For quartz-calcite-fluorite ore containing more calcite, quartz and calcite impurities need to be removed simultaneously in the ore dressing process, and qualified fluorite ore can be obtained. Because the same Ca is contained in the calcite and fluorite minerals ²⁺And the flotation agent has similar surface physical and chemical properties, and a good flotation index is difficult to obtain by adopting a conventional flotation process.

Chinese patent (publication No. CN 105289852A) discloses a method for carrying out acid leaching pretreatment and then carrying out flotation on high-calcium fluorite ore, wherein the acid leaching treatment is carried out on the high-calcium fluorite ore, and then the high-grade fluorite ore can be obtained by carrying out flotation. The acid leaching method has high requirements on equipment and can generate a large amount of acidic liquid. The Chinese patent (publication number: CN1032631A) carbonate-fluorite ore flotation separation method provides a flotation separation method using acidified water glass as an inhibitor. In Chinese patent (publication No. CN 102921551A), a fluorite ore flotation method uses water glass and sodium fluoride as combined inhibitors to obtain better flotation effect. The application of hydroxyethyl starch ether in fluorite ore floatation in Chinese patent (publication number: CN105817341A) takes the hydroxyethyl starch ether as a calcite inhibitor. The application of the Chinese patent (publication number: CN 105709939A) hydroxypropyl starch ether in fluorite ore flotation uses the hydroxypropyl starch ether as a calcite inhibitor. Chinese patent (publication No. CN102294296A) discloses a flotation separation method for controlling the floating of gangue by using a targeted inhibitor and carrying out centralized treatment on middlings in the previous two times.

The acid leaching or inhibiting method is effective for fluorite ore with low calcite content, and the fluorite ore with high calcite content has low separation efficiency, so that calcite gangue is difficult to be effectively separated, and high-grade fluorite ore cannot be obtained.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a novel flotation process which comprises the following steps: according to the process, quartz and calcite gangue can be effectively removed through positive and negative flotation, and high-grade fluorite concentrate is obtained.

The technical problem to be solved by the invention can be realized by the following technical scheme. The invention relates to a direct-reverse flotation process of quartz-calcite fluorite ore, which comprises the following steps: removing quartz gangue by direct flotation, and removing calcite gangue by reverse flotation to finally obtain fluorite concentrate.

In the invention, the removal of the quartz gangue by direct flotation can adopt the following steps: crushing and grinding quartz-calcite fluorite ore until mineral monomers are dissociated, adding water for size mixing to a certain concentration, then flowing into a stirring tank, respectively adding a proper amount of regulator, inhibitor and positive flotation collector into the ore pulp for size mixing, feeding the material subjected to size mixing into a positive flotation system for positive flotation roughing, wherein the product in the tank is tailings, the roughing foam product is refined for 1-10 times, the refining times are preferably 2-5 times, and the tailings subjected to positive flotation refining are returned to the previous flotation operation step by step.

In the invention, the reverse flotation for removing calcite gangue can adopt the following steps: and (3) feeding the selected foam into a reverse flotation stirring tank, respectively adding a proper amount of reverse flotation regulator, inhibitor and reverse flotation collector slurry, feeding the slurry-mixed material into a reverse flotation system for performing reverse flotation on calcite minerals, wherein the product in the tank is fluorite concentrate, scavenging the foam product for 1-10 times, preferably for 2-5 times, and returning the reverse flotation scavenged concentrate to the previous flotation operation step by step.

Wherein, the positive flotation collector is fatty acid, fatty acid soap or a composition of the fatty acid soap and a surfactant.

The reverse flotation collector is alkylamine dimethyl phosphonic acid with a structural formula of RN (CH) ₂PO ₃H ₂) ₂R is C ₈～C ₁₈An alkyl group or an alkenyl group.

The pH value of the direct flotation pulp is 8-11, the preferable pH value is 9-10, and the regulator is selected from sodium carbonate, sodium hydroxide, potassium hydroxide or ammonia water, and the preferable sodium carbonate; the inhibitor is preferably water glass.

The pH value of the ore pulp subjected to reverse flotation is 4-6, the pH value is preferably 4.5-5.5, and the regulator is selected from sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid, preferably sulfuric acid; the inhibitor is preferably citric acid.

Adding inhibitor water glass in the direct flotation and concentration operation, wherein the adding amount is 0.1-0.8 kg/t, and the adding amount is preferably 0.3-0.6 kg/t;

preferably, the regulator sulfuric acid and the inhibitor citric acid are added in the reverse flotation scavenging operation, the addition amount of the sulfuric acid is 1.0-3.0 kg/t, preferably 1.5-2.5 kg/t, and the addition amount of the citric acid is 0.1-0.5 kg/t. The addition amount is preferably 0.2-0.4 kg/t.

When the content of calcite in raw ore is higher, quartz and calcite are inhibited by adopting different inhibitors, so that fluorite ore floats upwards, and high-grade fluorite concentrate cannot be obtained due to the fact that the physical properties and the chemical properties of the surfaces of the calcite and the fluorite are similar, and the calcite cannot be effectively inhibited under the alkaline condition, and the separation efficiency is low. According to the properties of ores, fluorite and calcite are subjected to mixed flotation, and calcite is subjected to reverse flotation under an acidic condition, so that the aim of removing calcite from the bulk concentrate is fulfilled.

Compared with the prior art, the direct-reverse flotation process provided by the invention has the advantages of high separation efficiency and excellent process index aiming at quartz-calcite fluorite ore, lower calcite content in the obtained fluorite concentrate, higher concentrate quality, easiness in filtering the fluorite concentrate and the like.

Drawings

FIG. 1 is a process flow diagram of the process of the present invention in which there are three positive flotation beneficiating and two negative flotation scavenger steps.

Detailed Description

The invention is further illustrated by, but is not limited to, the following examples.