阅读说明：本技术 通过酸浸回收尾矿资源的硅钙质胶磷矿正反浮选工艺 (Silicon-calcium collophanite forward-reverse flotation process for recovering tailing resources through acid leaching ) 是由 李丰 宋文义 曹效权 钱押林 于 2018-08-07 设计创作，主要内容包括：本发明是一种通过酸浸回收尾矿资源的硅钙质胶磷矿正反浮选工艺,其步骤如下：将破碎好的硅钙质胶磷矿给入磨矿作业,待磨矿细度实现有用矿物和脉石矿物达到单体解离后给入浮选作业；浮选作业采用正反浮选或者反正浮选工艺流程；将正浮选脱硅作业的尾矿进行酸浸作业,浸出液过滤除渣后,上清液返回反浮选脱镁作业；酸浸作业所用的酸为无机强酸、有机强酸中的一种或者二者的混合物。本发明工艺简单、稳定,通过磷尾矿生产混酸返回至磷矿反浮选除镁作业中,真正的实现了变废为宝的目的,大大降低了磷尾矿的排放,且降低了浓硫酸的消耗,在节能减排方面具有很大的应用前景。(The invention relates to a silicon-calcium collophanite positive and negative flotation process for recovering tailing resources through acid leaching, which comprises the following steps: feeding the crushed silicon-calcium collophanite into ore grinding operation, and feeding the crushed silicon-calcium collophanite into flotation operation after useful minerals and gangue minerals reach monomer dissociation after the ore grinding fineness is realized; the flotation operation adopts a positive and negative flotation or a positive and negative flotation process flow; performing acid leaching operation on the tailings obtained in the positive flotation desiliconization operation, filtering and deslagging a leaching solution, and returning supernatant to the reverse flotation demagging operation; the acid used in the acid leaching operation is one of inorganic strong acid and organic strong acid or a mixture of the inorganic strong acid and the organic strong acid. The method has simple and stable process, and the mixed acid produced by the phosphate tailings is returned to the reverse flotation magnesium removal operation of the phosphate ore, so that the aim of changing waste into valuable is really fulfilled, the discharge of the phosphate tailings is greatly reduced, the consumption of concentrated sulfuric acid is reduced, and the method has great application prospects in the aspects of energy conservation and emission reduction.)

1. A silicon-calcium collophanite positive and negative flotation process for recovering tailing resources through acid leaching is characterized in that: the method comprises the following steps:

(1) feeding the crushed silicon-calcium collophanite into ore grinding operation, and feeding the crushed silicon-calcium collophanite into flotation operation after useful minerals and gangue minerals reach monomer dissociation after the ore grinding fineness is realized; the flotation operation adopts a positive and negative flotation or a positive and negative flotation process flow;

(2) performing acid leaching operation on the tailings obtained in the positive flotation desiliconization operation, filtering and deslagging a leaching solution, and returning supernatant to the reverse flotation demagging operation; the acid used in the acid leaching operation is one of inorganic strong acid and organic strong acid or a mixture of the inorganic strong acid and the organic strong acid.

2. The silico-calcic collophanite forward and reverse flotation process for recycling tailing resources through acid leaching according to claim 1, characterized in that: in the step (2), the acid leaching operation adopts one-step acid leaching or multi-step acid leaching.

3. The silico-calcic collophanite forward and reverse flotation process for recycling tailing resources through acid leaching according to claim 1, characterized in that: in the step (2), the inorganic strong acid is a mixed acid consisting of more than one of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid; the organic strong acid is one or a mixture of oxalic acid and citric acid.

4. The silico-calcic collophanite forward and reverse flotation process for recycling tailing resources through acid leaching according to claim 1, characterized in that: in the step (2), the acid used in the acid leaching operation is at least one of oxalic acid and citric acid, or a strong acid mixture consisting of at least one of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid is added.

5. The silico-calcic collophanite forward and reverse flotation process for recycling tailing resources through acid leaching according to claim 4, characterized in that: the mass concentration of the acid solution is 15-98%.

6. The silico-calcic collophanite forward and reverse flotation process for recycling tailing resources through acid leaching according to claim 5, characterized in that: the mass concentration of the acid solution is 20-45%.

7. The silico-calcic collophanite forward and reverse flotation process for recycling tailing resources through acid leaching according to claim 1, characterized in that: in the step (2), the liquid-solid ratio of the tailings to the ore pulp prepared from the acid is 2: 1-14: 1.

8. The silico-calcic collophanite forward and reverse flotation process for recycling tailing resources through acid leaching according to claim 7, characterized in that: in the step (2), the liquid-solid ratio of the tailings to the ore pulp prepared from the acid is 5: 1-10: 1.

9. The silico-calcic collophanite forward-reverse flotation process for recycling tailing resources through acid leaching according to any of the claims 1-8, characterized in that: the grinding fineness of the ore in the step (1) is-200 meshes and accounts for 72-95%.

10. The silico-calcic collophanite forward-reverse flotation process for recycling tailing resources through acid leaching according to any of the claims 1-8, characterized in that: the tailings in the step (2) mainly comprise the following components in percentage by weight: p₂O₅8.0~17.0%，MgO0.5~2.0%，SiO₂31.0-59.0%, and the balance of impurities.

Technical Field

The invention belongs to the technical field of mineral processing, and particularly relates to a silicon-calcium collophanite direct and reverse flotation process for recovering tailing resources through acid leaching.

Background

The phosphorite resources in China are very rich, the basic reserves of the resources are the second place in the world, but more than 94 percent of the phosphorite resources are medium and low grade phosphorite, and the ores can meet the requirements of downstream operation only by separating carbonate gangue and silicate gangue simultaneously. At present, aiming at low-grade calcium siliceous collophanite, two flotation processes, namely a positive-reverse flotation process and a reverse-positive flotation process, are commonly used, no matter which process is adopted, a demagging reverse flotation operation is required, the reverse flotation operation generally adopts sulfuric acid or mixed acid of sulfuric acid and phosphoric acid as an inhibitor of phosphorus minerals, if single sulfuric acid is adopted as the inhibitor of the reverse flotation, the problems of poor selectivity, complex process flow, more operation quantity and chemical adding points, large sulfuric acid consumption, difficult operation control, serious scaling of equipment pipelines and the like exist, and the mixed acid is adopted as the inhibitor, so that the method has the advantage of good flotation production indexes, but the chemical cost of the reverse flotation operation is higher due to higher price of the phosphoric acid. Therefore, how to reasonably develop and utilize the silico-calcium collophanite has important economic benefit and social significance for activating a large amount of silico-calcium collophanite resources in China at present.

Disclosure of Invention

The invention aims to solve the technical problem of the prior art, provides a novel silicon-calcium collophanite forward-reverse flotation process for recovering tailing resources through acid leaching, successfully solves the problems of large medicament dosage, general flotation selectivity, serious scaling of ore pulp pipelines and the like when part of phosphorite directly adopts sulfuric acid as an inhibitor, and greatly reduces the use amount of sulfuric acid in reverse flotation operation by using part of collophanite tailings produced by a dressing plant as raw materials to produce a reverse flotation inhibitor.

The technical problem to be solved by the present invention is achieved by the following technical means. The invention relates to a silicon-calcium collophanite positive and negative flotation process for recovering tailing resources by acid leaching, which is characterized in that: the method comprises the following steps:

(1) feeding the crushed silicon-calcium collophanite into ore grinding operation, and feeding the crushed silicon-calcium collophanite into flotation operation after useful minerals and gangue minerals reach monomer dissociation after the ore grinding fineness is realized; the flotation operation adopts a positive and negative flotation or a positive and negative flotation process flow;

(2) performing acid leaching operation on the tailings obtained in the positive flotation desiliconization operation, filtering and deslagging a leaching solution, and returning supernatant to the reverse flotation demagging operation; the acid used in the acid leaching operation is one of inorganic strong acid and organic strong acid or a mixture of the inorganic strong acid and the organic strong acid.

The invention relates to a silicon-calcium collophanite positive and negative flotation process for recovering tailing resources by acid leaching, which further adopts the preferable technical scheme that: in the step (2), the acid leaching operation adopts one-step acid leaching or multi-step acid leaching.

The invention relates to a silicon-calcium collophanite positive and negative flotation process for recovering tailing resources by acid leaching, which further adopts the preferable technical scheme that: in the step (2), the inorganic strong acid is a mixed acid consisting of more than one of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid; the organic strong acid is one or a mixture of oxalic acid and citric acid.

The invention relates to a silicon-calcium collophanite positive and negative flotation process for recovering tailing resources by acid leaching, which further adopts the preferable technical scheme that: in the step (2), the acid used in the acid leaching operation is at least one of oxalic acid and citric acid, or a strong acid mixture consisting of at least one of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid is added.

The invention relates to a silicon-calcium collophanite positive and negative flotation process for recovering tailing resources by acid leaching, which further adopts the preferable technical scheme that: the mass concentration of the acid solution is preferably 15-98%. .

The invention relates to a silicon-calcium collophanite positive and negative flotation process for recovering tailing resources by acid leaching, which further adopts the preferable technical scheme that: in the step (2), the liquid-solid ratio of the tailings to the ore pulp prepared from the acid is 2: 1-14: 1, preferably 5: 1-10: 1.

The invention relates to a silicon-calcium collophanite positive and negative flotation process for recovering tailing resources by acid leaching, which further adopts the preferable technical scheme that: the grinding fineness of the ore in the step (1) is-200 meshes and accounts for 72-95%.

The invention relates to a silicon-calcium collophanite positive and negative flotation process for recovering tailing resources by acid leaching, which further adopts the preferable technical scheme that: the tailings in the step (2) mainly comprise the following components in percentage by weight: p₂O₅8.0~17.0%，MgO 0.5~2.0%，SiO₂31.0-59.0%, and the balance of impurities.

The invention relates to a silicon-calcium collophanite positive and negative flotation process for recovering tailing resources by acid leaching, which further adopts the preferable technical scheme that: a silicon-calcium collophanite positive and negative flotation acid leaching treatment process comprises the following steps:

(1) feeding the crushed silicon-calcium collophanite into ore grinding operation, and feeding the crushed silicon-calcium collophanite into flotation operation after useful minerals and gangue minerals reach monomer dissociation after the ore grinding fineness is achieved, wherein the ore grinding fineness is 72-95% of-200 meshes;

(2) the flotation process flow adopted by the ore of the type can be any one of positive and negative flotation and negative and positive flotation process flows;

(3) wherein, the tailings of the positive flotation desiliconization operation are fed into an acid leaching tank;

(4) the acid leaching operation can be divided into one-step acid leaching or multi-step acid leaching, and the acid can be inorganic strong acid such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and the like, or organic strong acid such as oxalic acid and the like; or a mixed acid of an organic acid and an inorganic strong acid is adopted;

(5) after the leachate is filtered and deslagged, the supernatant returns to the reverse flotation demagging operation.

The main component of the phosphorite direct flotation tailings in the method contains P according to weight percentage₂O₅8.0~17.0%，MgO0.5~2.0%，SiO₂31.0-59.0%, and a small amount of other impurities; the grade P of the phosphate concentrate obtained by the method of the invention₂O₅28.0-33.9%, and the recovery rate of the obtained phosphate concentrate can reach 70.0-89.0% by weight.

The principle of the invention is as follows: p in tailings of silicon-calcium collophanite direct flotation₂O₅The grade of the tailings is about 12 percent generally, and the tailings P are difficult to be selected₂O₅The grade of the phosphate rock is higher, if the part of tailings is directly discarded, the waste of phosphate rock resources can be caused, the main minerals contained in the tailings of siliceous collophanite or the tailings of silico-calcareous collophanite direct flotation are fluorine-based apatite, quartz and some silicates, and because only the fluorine-based apatite of the three ores is easily dissolved in strong acid and the solubility of the quartz and some silicates in the strong acid is lower, the phosphorus in the fluorine-based apatite is extracted by the strong acid to prepare the mixed solution of the strong acid and phosphoric acid. The equation is as follows:

2Ca₅F（PO₄）₃+20H⁺+H₂O=6H₃PO₄+10Ca²⁺+2HF+ H₂O

compared with the prior art, the technical scheme of the invention has the following advantages:

(1) the comprehensive utilization of the phosphate tailings is well realized, the waste is really changed into valuable, and the discharge of the phosphate tailings is reduced;

(2) the phosphate tailings can be used as a preparation raw material of an inhibitor for the reverse flotation and magnesium removal operation of the collophanite, the prepared collecting agent can be mixed with concentrated sulfuric acid and added to the reverse flotation operation, compared with the prior art that single sulfuric acid is used as the inhibitor, the collecting agent has the advantages of good flotation and separation indexes, low dosage of sulfuric acid agents and reduced scaling phenomenon of a flotation machine and an ore pulp pipeline.

(3) The waste residue of the acid leaching tank can be used for producing cement, thereby really realizing zero emission.

(4) The invention successfully solves the problems of large medicament dosage, common flotation selectivity, serious scaling of an ore pulp pipeline and the like existing when part of phosphorite directly adopts sulfuric acid as an inhibitor, reduces the discharge of phosphorus tailings by utilizing a part of collophanite tailings produced by a dressing plant as a raw material to produce a reverse flotation inhibitor, and greatly reduces the use amount of sulfuric acid in the reverse flotation operation and can bring considerable economic benefits for enterprises by using the newly generated inhibitor to perform reverse flotation operation, thereby achieving the test index of adopting phosphoric acid and sulfuric acid as mixed acid as the inhibitor.

The specific implementation mode is as follows:

the following further describes particular embodiments of the present invention to facilitate further understanding of the present invention by those skilled in the art, and does not constitute a limitation to the right thereof.