阅读说明：本技术 一种磷矿反浮选脱硅铝捕收剂及其制备方法和用途 (Reverse flotation desilication aluminum collecting agent for phosphorite and preparation method and application thereof ) 是由 李松清 孙昊 胡晓星 郑桂兵 朱阳戈 崔强 肖婉琴 宋振国 周兵仔 任爱军 于 2019-11-01 设计创作，主要内容包括：本发明涉及一种磷矿反浮选脱硅铝捕收剂及其制备方法和用途,所述捕收剂包含：混合胺、混合醇和椰油酸甲酯；本发明中提供的磷矿反浮选脱硅铝捕收剂具有浮选性能良好、耐低温、药剂成本适中、适用浮选pH范围较宽(介于5-10)等优点；同时利用所述捕收剂进行浮选时也有矿化泡沫较脆、流动性良好等优点。反浮选作业中,脱硅铝时只需采用该捕收剂即可,使得浮选药剂种类减少,同时所述脱硅铝捕收剂对脱镁捕收剂反浮选脱镁的影响不明显,回水全部回用难度小。(The invention relates to a reverse flotation desilication aluminum collecting agent for phosphorite, a preparation method and application thereof, wherein the collecting agent comprises the following components: mixed amines, mixed alcohols and methyl cocoate; the reverse flotation desilication aluminum collecting agent for the phosphorite provided by the invention has the advantages of good flotation performance, low temperature resistance, moderate medicament cost, wide applicable flotation pH range (between 5 and 10) and the like; meanwhile, the collecting agent has the advantages of brittle mineralized foam, good fluidity and the like when being used for flotation. In the reverse flotation operation, only the collecting agent is needed to be adopted during desiliconization, so that the types of flotation reagents are reduced, meanwhile, the influence of the desiliconized collecting agent on reverse flotation demagging is not obvious, and the difficulty in recycling all return water is small.)

1. A reverse flotation desilicated collector for phosphate ore, comprising: mixed amines, mixed alcohols and methyl cocoate.

2. A collector of claim 1, comprising the following components in parts by weight: 4-6 parts of mixed amine; 1-3 parts of mixed alcohol; 1-5 parts of cocoate methyl ester.

3. A collector according to claim 1 or 2, wherein the content of mixed amine in the collector is 4.4-5.6 parts by weight, preferably 4.8-5.2 parts by weight;

preferably, the content of the mixed alcohol in the collector is 1.4-2.6 parts by weight, preferably 1.8-2.2 parts by weight;

preferably, the cocoate methyl ester content of the collector is from 1.4 to 4.5 parts by weight, preferably from 2 to 4 parts by weight.

4. A collector as claimed in any one of claims 1 to 3 wherein the mixed amines include decaalkyl ether amines, dodecyl ether amines and tetradecyl ether amines;

preferably, the mixed alcohols include n-octanol, iso-octanol, and decanol.

5. A collector as claimed in claim 4, in which the mixed amine has a content of the dodecyl ether amine of from 0.1 to 0.5 parts by weight, preferably from 1.5 to 4.5 parts by weight;

preferably, the content of the dodecyl ether amine in the mixed amine is 0.1 to 0.3 part by weight, preferably 1.4 to 2.4 parts by weight;

preferably, the mixed amine has a tetradecyl ether amine content of 0.4 to 0.6 parts by weight, preferably 4.2 to 5.5 parts by weight.

6. A collector according to claim 4 or 5, characterised in that the content of n-octanol in the mixed alcohol is 5 to 7 parts by weight, preferably 5.5 to 6.5 parts by weight;

preferably, the isooctanol content of the mixed alcohol is from 1 to 2 parts by weight, preferably from 1.4 to 1.8 parts by weight;

preferably, the content of the decanol in the mixed alcohol is 1 to 4 parts by weight, preferably 2 to 3 parts by weight.

7. The method of preparing a reverse flotation desilicated aluminum collector for phosphorus ore according to any one of claims 1 to 6, wherein the method of preparing comprises: respectively preparing mixed amine and mixed alcohol, and then mixing the obtained mixed amine and mixed alcohol with coconut oil methyl ester to obtain the collector.

8. The method of claim 7, comprising the steps of:

(1) mixing the dodecyl ether amine, the dodecyl ether amine and the tetradecyl ether amine, and uniformly stirring to obtain mixed amine;

(2) mixing n-octanol, isooctanol and decanol, and uniformly stirring to obtain mixed alcohol;

(3, mixing the mixed amine prepared in the step (1), the mixed alcohol prepared in the step (2) and coconut methyl ester, and uniformly stirring to obtain the collector.

9. The method of claim 7 or 8, comprising the steps of:

(1) mixing 1-5 parts by weight of dodecyl ether amine, 1-3 parts by weight of dodecyl ether amine and 4-6 parts by weight of tetradecyl ether amine, and uniformly stirring to obtain mixed amine;

(2) mixing 5-7 parts by weight of n-octanol, 1-2 parts by weight of isooctanol and 1-4 parts by weight of decanol, and uniformly stirring to obtain mixed alcohol;

(3) and (3) mixing 4-6 parts by weight of mixed amine prepared in the step (1), 1-3 parts by weight of mixed alcohol prepared in the step (2) and 1-5 parts by weight of methyl cocoate, and uniformly stirring to obtain the collector.

10. Use of the reverse flotation desilicated aluminum collector for phosphorite according to any one of claims 1 to 6, characterized in that it is used for desilicated aluminum in phosphorite single/double reverse flotation process.

Technical Field

The invention relates to the field of phosphorite flotation, relates to a reverse flotation desilication aluminum collecting agent for phosphorite, and a preparation method and application thereof, and particularly relates to a collecting agent suitable for removing silicon-containing minerals and aluminum-containing gangue by reverse flotation of medium and low grade phosphorite, and a preparation method and application thereof.

Background

70 percent of phosphorite resources in China belong to sedimentary rock type phosphorite, are mainly distributed in clouds, nobility, Sichuan, Xiang and Hubei, and medium-low grade silico-calcium high-sesquioxide phosphorite also needs to be developed and utilized as easily-selected medium-high grade magnesium phosphorite is completely exploited. Aiming at the medium-low grade refractory collophanite resource, the currently developed mineral separation processes mainly comprise forward-reverse flotation, double-reverse flotation, gravity separation and flow division, coarse separation, coarse particle double-reverse flotation, fine particle forward-reverse flotation, desliming, forward-reverse flotation, reverse-forward flotation and the like, wherein the forward-reverse flow is most likely to be industrialized, but the selection of enterprises is difficult due to the problems of high mineral separation cost, multiple medicament types, difficult backwater utilization and the like. Theoretically, the double reverse flotation is the most suitable mineral separation process for medium and low grade collophanite, but the industrialization is difficult to realize due to the lack of a reverse flotation desilicated aluminum collector with excellent flotation performance, lower medicament cost, better natural defoaming performance and better mineralized foam fluidity. Reverse flotation collectors as mentioned in CN103286007A, although they can also achieve the same or similar results as phosphate concentrates, are directed to phosphate concentrates after demagging, limiting their scope of use. For example, in CN104888968A, a plurality of reagents such as sulfuric acid, lemonade, and water glass need to be added during the flotation process, and the types of reagents are many, which significantly increases the ore dressing cost and the difficulty in utilizing the return water. Therefore, a reverse flotation desilicated aluminum collector with excellent flotation performance, lower medicament cost, better natural defoaming performance, better mineralized foam fluidity and wide utilization range is needed at present.

Disclosure of Invention

In view of the problems in the prior art, the invention aims to provide a desilicated aluminum collector for reverse flotation of phosphate ore, a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a reverse flotation desilicated aluminum collector for phosphate ore, the collector comprising: mixed amines, mixed alcohols and methyl cocoate;

according to the invention, the mixed amine, the mixed alcohol and the coconut methyl ester are compounded, and a synergistic interaction effect can be achieved among the mixed amine, the mixed alcohol and the coconut methyl ester, so that the provided reverse flotation desiliconized aluminum collecting agent for the phosphorite has the advantages of good flotation performance, low temperature resistance, moderate medicament cost, wide applicable flotation pH range (between 5 and 10) and the like; meanwhile, the collecting agent is utilized to carry out flotation, and the advantages of brittle mineralized foam, good fluidity and the like are achieved. In the reverse flotation operation, only the collecting agent is needed to be adopted during desiliconization, so that the types of flotation reagents are reduced, meanwhile, the influence of the desiliconized collecting agent on reverse flotation demagging is not obvious, and the difficulty in recycling all return water is small. The collecting agent has very important significance for economic development and utilization of a large amount of middle-low grade silico-calcium high-sesquioxide phosphorite in phosphorite enterprises in China.

As a preferable technical scheme, the collector comprises the following components in parts by weight:

the amount of the mixed amine is 4 to 6 parts, for example, 4 parts, 4.2 parts, 4.4 parts, 4.6 parts, 4.8 parts, 5 parts, 5.2 parts, 5.4 parts, 5.6 parts, 5.8 parts or 6 parts, but is not limited to the above-mentioned values, and other values not listed in the present range are also applicable.

The mixed alcohol may be 1 to 3 parts, for example, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts or 3 parts, but is not limited to the above-mentioned values, and other values not listed in the present range are also applicable.

The amount of methyl cocoate is, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, but is not limited to the above-mentioned values, and other values not listed in the present range are also applicable.

In a preferred embodiment of the present invention, the content of the mixed amine in the collector is 4.4 to 5.6 parts by weight, preferably 4.8 to 5.2 parts by weight.

Preferably, the content of the mixed alcohol in the collector is 1.4-2.6 parts by weight, preferably 1.8-2.2 parts by weight.

Preferably, the cocoate methyl ester content of the collector is from 1.4 to 4.5 parts by weight, preferably from 2 to 4 parts by weight.

As a preferred technical scheme of the invention, the mixed amine comprises dodecyl ether amine, dodecyl ether amine and tetradecyl ether amine.

Preferably, the mixed alcohols include n-octanol, iso-octanol, and decanol.

In a preferred embodiment of the present invention, the content of the decaalkyl ether amine in the mixed amine is 1 to 5 parts by weight, and may be, for example, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, or 5 parts by weight, but is not limited to the above-mentioned values, and other values not listed in the present range are also applicable, and preferably 1.5 to 4.5 parts by weight.

Preferably, the content of the dodecyl ether amine in the mixed amine is 1 to 3 parts by weight, and may be, for example, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight, 2.8 parts by weight, or 3 parts by weight, but is not limited to the listed values, and other values not listed in the present range are also applicable, and preferably 1.4 to 2.4 parts by weight.

Preferably, the mixed amine contains tetradecyl ether amine in an amount of 4 to 6 parts by weight, for example, 4 parts by weight, 4.2 parts by weight, 4.4 parts by weight, 4.6 parts by weight, 4.8 parts by weight, 5 parts by weight, 5.2 parts by weight, 5.4 parts by weight, 5.6 parts by weight, 5.8 parts by weight, or 6 parts by weight, but the content is not limited to the listed values, and other values not listed in the present range are also applicable, preferably 4.2 to 5.5 parts by weight.

In a preferred embodiment of the present invention, the content of n-octanol in the mixed alcohol is 5 to 7 parts by weight, and may be, for example, 5 parts by weight, 5.2 parts by weight, 4.5 parts by weight, 5.6 parts by weight, 5.8 parts by weight, 6 parts by weight, 6.2 parts by weight, 6.4 parts by weight, 6.6 parts by weight, 6.8 parts by weight, or 7 parts by weight, but the present invention is not limited to the listed values, and other values not listed in the present range are also applicable.

Preferably, the mixed alcohol has an isooctanol content of 1 to 2 parts by weight, 1 part by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, or 2 parts by weight, and the like, and is not limited to the values listed, and other values not listed in the present range are also applicable.

Preferably, the mixed alcohol contains decanol in an amount of 1 to 4 parts by weight, and may be, for example, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.4 parts by weight, 3.6 parts by weight, 3.8 parts by weight, or 4 parts by weight, but is not limited to the listed values, and other values not listed in the present range are also applicable.

According to the invention, through reasonable selection of the components in the collecting agent and the proportion thereof, the components in the collecting agent are properly adsorbed on the surface of the mineral, and mineralized foam with difficultly-eliminated solid property is prevented from being formed by excessive adsorption on the surface of the mineral in the collecting agent, so that the hydrophobic modification of the silicon-aluminum-containing mineral in flotation is ensured, the brittleness and the fluidity of the mineralized foam are increased, and the efficient flotation performance of the collecting agent in the flotation process is realized. Meanwhile, the collector has better mobility in ore pulp and can be used at lower temperature; the cost for preparing the collecting agent is reasonably controlled due to the reasonable selection of the raw materials; furthermore, the collector is applicable to a wider flotation range (5-10), so that the collector does not need to adjust the pH value of ore pulp in the use process, and the use range of the collector is expanded; meanwhile, other agents are not required to be added in the using process, so that the utilization of the return water is simplified, and the return water can be returned to the flotation process or the ore grinding process for use without treatment basically.

In a second aspect, the present invention provides a method of making a reverse flotation desilicated aluminum collector for phosphate ore according to the first aspect, the method comprising: respectively preparing mixed amine and mixed alcohol, and then mixing the obtained mixed amine and mixed alcohol with coconut oil methyl ester to obtain the collector.

As a further preferable technical scheme of the invention, the preparation method comprises the following steps:

(1) mixing the dodecyl ether amine, the dodecyl ether amine and the tetradecyl ether amine, and uniformly stirring to obtain mixed amine;

(2) mixing n-octanol, isooctanol and decanol, and uniformly stirring to obtain mixed alcohol;

(3, mixing the mixed amine prepared in the step (1), the mixed alcohol prepared in the step (2) and coconut methyl ester, and uniformly stirring to obtain the collector.

As a preferred technical scheme of the invention, the preparation method comprises the following steps:

(1) mixing 1-5 parts by weight of dodecyl ether amine, 1-3 parts by weight of dodecyl ether amine and 4-6 parts by weight of tetradecyl ether amine, and uniformly stirring to obtain mixed amine;

(2) mixing 5-7 parts by weight of n-octanol, 1-2 parts by weight of isooctanol and 1-4 parts by weight of decanol, and uniformly stirring to obtain mixed alcohol;

(3) and (3) mixing 4-6 parts by weight of mixed amine prepared in the step (1), 1-3 parts by weight of mixed alcohol prepared in the step (2) and 1-5 parts by weight of methyl cocoate, and uniformly stirring to obtain the collector.

In the invention, the mixing proportion of each component in the collecting agent is selected according to the factors such as the type, proportion, fineness and the like of each mineral in a mineral separation system, and meanwhile, in the preparation process of the collecting agent, different raw materials are mixed and stirred uniformly at room temperature in sequence, so that the collecting agent is simple in mixing process, free of heating and low in cost.

In a third aspect, the invention provides a use of the reverse flotation desilicated aluminum collector for phosphorite as described in the first aspect, which is used for desilicated aluminum in phosphorite single/double reverse flotation process.

In the invention, the phosphorite is subjected to double reverse flotation operation after ore grinding and grading overflow, wherein the double reverse flotation operation comprises reverse flotation of silicon and aluminum and reverse flotation of magnesium. In the reverse flotation of silicon and aluminum and the reverse flotation of magnesium, multiple roughing, concentration and scavenging operations can be set according to the properties of actual raw ores, and the indexes of the required phosphate concentrate are achieved.

Compared with the prior art, the invention at least has the following beneficial effects:

(1) the collector for reverse flotation desilication of the phosphorite not only has the advantages of good flotation performance, low temperature resistance (15-25 ℃), moderate medicament cost, wide applicable flotation pH range (between 5 and 10) and the like, but also has the advantages of brittle mineralized foam, good fluidity and the like in the flotation process.

(2) In the double-reverse flotation process, only a certain amount of collecting agent provided by the invention needs to be added in the desiliconization stage, and other agents do not need to be added, namely the types of flotation agents are few; meanwhile, the desiliconized aluminum collector provided by the invention has no obvious influence on reverse flotation and demagging of the demagging collector, and the difficulty in recycling all return water is small.

(3) In the double reverse flotation process, the desiliconized aluminum collecting agent provided by the invention can be used for obtaining phosphate concentrate with the grade of 28-34% in desiliconized aluminum flotation operation, wherein P is₂O₅The recovery rate can reach 82.65%.

Detailed Description

To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows: