CN103909019A - Anion collecting agent for reverse flotation of Anshan type lean hematite ore at normal temperature - Google Patents

Abstract

The invention provides an anion collecting agent for reverse flotation of Anshan type lean hematite ore at a normal temperature. The anion collecting agent is composed of C16H31COCH(COONa)2 and one or more of ricinoleic acid, vegetable oleic acid, animal oleic acid or cottonseed oleic acid, wherein C16H31- refers to linear chain alkenyl with unsaturated double bonds within C7-8. Flotation at the normal temperature can be realized by the anion collecting agent, the flotation pulp temperature is lowered from 40-45DEG C to 17-18DEG C and lowered by 25DEG C on average, flotation index can be remarkably improved, flotation concentrate grade is increased by 0.15 percentage point on average, flotation tailings grade is lowered by 1.27 percentage points on average, and metal recovery rate is increased by 2.09 percentage points on average.

Description

An anion collector for reverse flotation of Anshan type lean hematite at normal temperature

technical field

The invention relates to an anion collector for reverse flotation of Anshan type lean hematite at normal temperature.

Background technique

At present, anion reverse flotation process is widely used to produce high-quality iron ore concentrate by using Anshan-style lean hematite ore. Among them, the anion reverse flotation process of Anshan Iron and Steel Group Mining Company East Anshan Sintering Plant is more commonly used KS-III Anion collectors or industrial oleic acid anion collectors can obtain flotation concentrates with an iron grade of about 66%, and discard flotation tailings with an iron grade of more than 25%. The commonly used process pulp must be heated. In order to improve the grade of the flotation concentrate, the temperature of the pulp is gradually raised in actual production, from the original design of 30°C to the current commonly used 40°C above, resulting in Energy consumption and costs have risen sharply. The reason is that KS-III collector or industrial oleic acid anion collector is very sensitive to the temperature of the pulp, the higher the temperature of the pulp, the stronger the activity of the agent, the better the dispersibility, and the more conducive to improving the grade of the concentrate. In addition, the flotation foam produced in the high temperature reverse flotation process is relatively viscous, which entrains a part of fine-grained iron minerals in the foam, resulting in an increase in the grade of flotation tailings.

In order to reduce the energy consumption and cost of the flotation process, and to improve the flotation index, an anion collector suitable for reverse flotation of ore pulp at room temperature is needed.

Contents of the invention

The purpose of the present invention is to provide an anion collector for reverse flotation of Anshan type lean hematite at normal temperature.

According to the anion collector for reverse flotation of Anshan type lean hematite at normal temperature according to the present invention, it is characterized in that it contains C ₁₆ H ₃₁ COCH(COONa) ₂ ,

Wherein, C ₁₆ H ₃₁ - is a straight-chain alkenyl group having an unsaturated double bond between C _7-8 .

According to the anion collector for reverse flotation of Anshan type lean hematite at normal temperature according to the present invention, it is characterized in that it contains C ₁₆ H ₃₁ COCH(COONa) ₂ , and also contains ricinoleic acid, vegetable oleic acid, animal oil one or more of cottonseed oleic acid,

Wherein, C ₁₆ H ₃₁ - is a straight-chain alkenyl group having an unsaturated double bond between C _7-8 .

According to the anion collector for reverse flotation of Anshan type lean hematite at normal temperature according to the present invention, it is characterized in that, by mass percentage, it contains C ₁₆ H ₃₁ COCH(COONa) ₂ is 1-99% , and the rest are one or more of ricinoleic acid, vegetable oleic acid, animal oleic acid or cottonseed oleic acid,

Wherein, C ₁₆ H ₃₁ - is a straight-chain alkenyl group having an unsaturated double bond between C _7-8 .

The anion collector of the present invention carries out reverse flotation to Anshan type lean hematite ore under normal temperature, and is used for sorting East Anshan lean hematite ore. Compared with collectors or industrial oleic acid anion collectors, the cost is similar. However, the anion collector of the present invention for reverse flotation of Anshan-type lean hematite ore at normal temperature can be adapted to carry out reverse flotation at a temperature of 17° C. of ore pulp or at normal temperature, so as to reduce the energy consumption of the flotation process. The carbonyl group in the molecule and the oxygen in the carboxyl group, as well as the oxygen in the two carboxyl groups, can form a six-membered chelation with the metal ion on the surface of the activated gangue and combine to form a complex. Collector capacity and selectivity.

The KS-III anionic collector is disclosed by Patent No. 201010574922, and is one of the commercially available series of KS anionic collectors. The industrial oleic acid anion collector is also commercially available.

The results of laboratory sorting tests on Dong’anshan lean hematite ore show that normal temperature flotation can be realized, and the temperature of the flotation pulp is reduced from 40-45°C to 17-18°C, with an average reduction of 25°C, and can be significantly improved and increased. Flotation indicators, flotation concentrate grade increased by 0.15 percentage points on average, flotation tailings grade decreased by 1.27 percentage points on average, and metal recovery rate increased by 2.09 percentage points on average. The anion collector for performing reverse flotation on Anshan-type lean hematite at normal temperature has wide application prospects for similar ores.

Detailed ways

The following non-limiting examples and comparative examples can enable those skilled in the art to understand the present invention more fully, but do not limit the present invention in any way.

When carrying out reverse flotation, the mass percentage composition of sodium hydroxide aqueous solution is 5%; The mass percentage composition of starch aqueous solution is 2%; The mass percentage composition of calcium oxide aqueous solution is 2%; The mass percent content of the anion collector aqueous solution such as KS-III and the like for reverse flotation of formula lean hematite is 2%.

The wt% mentioned below refers to the mass percentage, and C ₁₆ H ₃₁ - is a straight-chain alkenyl group with unsaturated double bonds between C _7-8 .

The present invention contains C ₁₆ H ₃₁ COCH(COONa) ₂ and also contains one or more of ricinoleic acid, vegetable oleic acid, animal oleic acid or cottonseed oleic acid for reverse flotation of Anshan type lean hematite at normal temperature Anion collectors, hereinafter referred to as composite collectors.

Example 1:

The iron ore with a raw ore grade of 24.56% is subjected to three-stage and one closed-circuit crushing, stage grinding, coarse and fine separation, gravity separation and magnetic separation to obtain mixed magnetic concentrate for flotation test feed, with a grade of 45.54%. The laboratory adopts the XFD type 0.5L single-cell flotation machine, which is the flotation test equipment. Weigh 200 grams of the mixed magnetic fine sample into the 0.5L flotation tank, add water close to the scale, start the flotation machine, and then add 3.5 milliliters of sodium hydroxide aqueous solution, 11.5 milliliters of starch aqueous solution, 3.5 milliliters of calcium oxide aqueous solution and 12.0 milliliters of C ₁₆ H ₃₁ COCH (COONa) ₂ collector aqueous solution, under the condition of 16.9 ℃, carry out the defloating of one rough one fine three sweeps In the sorting test, the flotation concentrate grade was 66.31%, the flotation tailings grade was 21.57%, and the metal recovery rate was 78.01%.

Example 2:

The iron ore grade, beneficiation process and pretreatment operation were the same as in Example 1, and 3.5 milliliters of sodium hydroxide aqueous solution, 11.5 milliliters of starch aqueous solution, 3.5 milliliters of calcium oxide aqueous solution and 11.0 milliliters of C ₁₆ H ₃₁ COCH(COONa) were added _successively . Under the condition of 16.9°C, a reverse flotation separation test of one coarse, one fine and three sweeps was carried out, and finally the grade of flotation concentrate was 65.96%, the grade of flotation tailings was 21.39%, and the metal recovery rate was 78.48%.

Example 3:

With the iron ore grade, beneficiation process and pretreatment operation of Example 1, add successively 3.5 milliliters of sodium hydroxide aqueous solution, 11.2 milliliters of starch aqueous solution, 3.5 milliliters of calcium oxide aqueous solution and 11.2 milliliters of composite collector aqueous solution, and its composite collection C ₁₆ H ₃₁ COCH(COONa) ₂ 99wt% in the agent, ricinoleic acid 1wt%, under the condition of 17.7 ℃, carry out the reverse flotation sorting test of one rough one fine three sweeps, and finally obtain the flotation concentrate grade of 66.03% , Flotation tailings 21.99%, weight 61.5 grams, metal recovery rate 77.53%.

Example 4:

With the iron ore grade, beneficiation process and pretreatment operation of Example 1, add 3.5 milliliters of sodium hydroxide aqueous solution, 11.4 milliliters of starch aqueous solution, 3.5 milliliters of calcium oxide aqueous solution and 11.5 milliliters of composite collector aqueous solution successively, and its composite collection C ₁₆ H ₃₁ COCH(COONa) ₂ 95wt% in the agent, vegetable oleic acid 5wt%, under the condition of 17.5 ℃, carry out the reverse flotation sorting test of one coarse, one fine and three sweeps, and finally obtain the flotation concentrate grade of 65.60%, The flotation tailings product is 21.22%, and the metal recovery rate is 78.94%.

Example 5:

With the iron ore grade, beneficiation process and pretreatment operation of Example 1, add 3.5 milliliters of sodium hydroxide aqueous solution, 11.1 milliliters of starch aqueous solution, 3.5 milliliters of calcium oxide aqueous solution and 11.2 milliliters of composite collector aqueous solution successively, and its composite collector C ₁₆ H ₃₁ COCH(COONa) ₂ 75wt%, ricinoleic acid 5wt%, vegetable oleic acid 10wt%, animal oleic acid 5wt% and cottonseed oleic acid 5wt% in the agent, under the condition of 17.5 ℃, carry out one crude one fine three cleaning The reverse flotation sorting test finally obtained a flotation concentrate grade of 65.51%, a flotation tailings product of 21.55%, and a metal recovery rate of 78.50%.

Embodiment 6:

With the iron ore grade, beneficiation process and pretreatment operation of Example 1, add 3.5 milliliters of sodium hydroxide aqueous solution, 11.0 milliliters of starch aqueous solution, 3.5 milliliters of calcium oxide aqueous solution and 12.0 milliliters of composite collector aqueous solution successively, and its composite collection C ₁₆ H ₃₁ COCH(COONa) ₂ 86wt%, ricinoleic acid 6.5wt%, and vegetable oleic acid 7.5wt% in the agent, under the condition of 17.5 ℃, carry out the reverse flotation sorting test of one rough one fine three sweeps, and finally obtain The flotation concentrate grade is 65.84%, the flotation tailings product is 22.44%, and the metal recovery rate is 76.95%.

Embodiment 7:

With the iron ore grade, beneficiation process and pretreatment operation of Example 1, add 3.0 milliliters of sodium hydroxide aqueous solution, 11.5 milliliters of starch aqueous solution, 3.0 milliliters of calcium oxide aqueous solution and 12.0 milliliters of composite collector aqueous solution successively, and its composite collection 35wt% ricinoleic acid, 45wt% vegetable oleic acid and 20wt% C ₁₆ H ₃₁ COCH(COONa) ₂ in the agent, under the condition of 16.9 ℃, carry out the reverse flotation sorting test of one crude one fine three sweeps, and finally obtain the flotation The concentrate grade is 66.20%, the flotation tailings product is 23.65%, and the metal recovery rate is 74.78%.

Embodiment 8:

With the iron ore grade, beneficiation process and pretreatment operation of Example 1, 3.0 milliliters of sodium hydroxide aqueous solution, 11.5 milliliters of starch aqueous solution, 3.5 milliliters of calcium oxide aqueous solution and 11.0 milliliters of composite collector aqueous solution were added successively, and the composite collector C ₁₆ H ₃₁ COCH(COONa) ₂ 50wt%, ricinoleic acid 35wt%, and vegetable oleic acid 15wt% in the agent, under the condition of 17.5 ℃, carry out the reverse flotation sorting test of one rough one fine three sweeps, and finally obtain the flotation The concentrate grade is 65.52%, the flotation tailings product is 22.60%, and the metal recovery rate is 76.90%.

Embodiment 9:

With the iron ore grade, beneficiation process and pretreatment operation of Example 1, add 3.0 milliliters of sodium hydroxide aqueous solution, 12.0 milliliters of starch aqueous solution, 3.0 milliliters of calcium oxide aqueous solution and 11.5 milliliters of composite collector aqueous solution successively, and its composite collector C ₁₆ H ₃₁ COCH(COONa) ₂ 30wt%, ricinoleic acid 15wt% and vegetable oleic acid 55wt%, under the condition of 17.2 ℃, carry out the reverse flotation sorting test of one crude one fine three sweeps, and finally obtain the flotation concentrate The ore grade is 66.19%, the flotation tailings product is 23.90%, and the metal recovery rate is 74.37%.

Example 10:

With the iron ore grade, beneficiation process and pretreatment operation of Example 1, add 3.5 milliliters of sodium hydroxide aqueous solution, 11.5 milliliters of starch aqueous solution, 3.5 milliliters of calcium oxide aqueous solution and 12.0 milliliters of composite collector aqueous solution, and its composite collection C ₁₆ H ₃₁ COCH(COONa) ₂ 10wt%, soybean oil 40wt% and cottonseed oleic acid 50wt% in the agent, under the condition of 17.2 ℃, carry out the reverse flotation sorting test of one rough one fine three sweeps, and finally obtain the flotation The concentrate grade is 66.13%, the flotation tailings product is 23.98%, and the metal recovery rate is 74.28%.

Example 11:

With the iron ore grade, beneficiation process flow and pretreatment operation of Example 1, 3.5 milliliters of sodium hydroxide aqueous solution, 10.6 milliliters of starch aqueous solution, 3.5 milliliters of calcium oxide aqueous solution and 12.3 milliliters of composite collector aqueous solution were added successively, and its composite collector C ₁₆ H ₃₁ COCH(COONa) ₂ 8wt%, ricinoleic acid 36wt%, vegetable oleic acid 30wt% and animal oleic acid 26wt% in the agent, under the condition of 17.8 ℃, carry out reverse flotation sorting test , and finally obtained a flotation concentrate grade of 65.58%, a flotation tailings grade of 22.89%, and a metal recovery rate of 76.40%.

Example 12:

With the iron ore grade, beneficiation process flow and pretreatment operation of Example 1, 3.5 milliliters of sodium hydroxide aqueous solution, 10.6 milliliters of starch aqueous solution, 3.5 milliliters of calcium oxide aqueous solution and 12.3 milliliters of composite collector aqueous solution were added successively, and its composite collector C ₁₆ H ₃₁ COCH(COONa) ₂ 3wt% in the agent, ricinoleic acid 25wt%, vegetable oleic acid 37wt% and cottonseed oleic acid 35wt%, under the condition of 17.6 ℃, carry out reverse flotation sorting Through the test, the grade of flotation concentrate was 66.27%, the grade of flotation tailings was 24.13%, and the metal recovery rate was 73.93%.

Example 13:

With the iron ore grade, beneficiation process and pretreatment operation of Example 1, 3.5 milliliters of sodium hydroxide aqueous solution, 10.5 milliliters of starch aqueous solution, 3.5 milliliters of calcium oxide aqueous solution and 12.5 milliliters of composite collector aqueous solution were added successively, and its composite collector C ₁₆ H ₃₁ COCH(COONa) ₂ 5wt%, ricinoleic acid 55wt%, and tallow oleic acid 45wt% in the agent, under the condition of 17.2 ℃, carry out the reverse flotation sorting test of one rough one fine three sweeps, and finally obtain the flotation The concentrate grade is 65.64%, the flotation tailings grade is 23.94%, and the metal recovery rate is 74.66%.

Example 14:

The same beneficiation process and pretreatment operation as in Example 1, the iron ore floatation grade is 45.54%, sequentially add 3.0 milliliters of sodium hydroxide aqueous solution, 12.0 milliliters of starch aqueous solution, 2.5 milliliters of calcium oxide aqueous solution and 12.3 milliliters of composite collector aqueous solution , in the composite collector, C ₁₆ H ₃₁ COCH(COONa) ₂ 1wt%, ricinoleic acid 55wt% and soybean oilic acid 44wt%, under the condition of 17 ℃, carry out reverse flotation separation Through the test, the grade of flotation concentrate was 65.51%, the grade of flotation tailings was 23.75%, and the metal recovery rate was 75.06%.

Example 15:

The beneficiation process and pretreatment operation are the same as in Example 1. The iron ore floatation grade is 45.54%. Add 3.5 ml of sodium hydroxide aqueous solution, 12.0 ml of starch aqueous solution, 2.5 ml of calcium oxide aqueous solution and 12.3 ml of composite collector aqueous solution , in the composite collector, C ₁₆ H ₃₁ COCH(COONa) ₂ 40wt%, cottonseed oleic acid 35wt% and soybean oil oleic acid 25wt%, under the condition of 17.2 ℃, carry out reverse flotation sorting Through the test, the flotation concentrate grade was finally obtained at 66.49%, the flotation tailings product was 23.70%, and the metal recovery rate was 74.52%.

Example 16:

The beneficiation process and pretreatment operation are the same as in Example 1, the iron ore floatation grade is 45.54%, and 3.0 ml of sodium hydroxide aqueous solution, 12.0 ml of starch aqueous solution, 3.0 ml of calcium oxide aqueous solution and 12.3 ml of composite collector aqueous solution are added in sequence , in the composite collector, C ₁₆ H ₃₁ COCH(COONa) ₂ 15wt%, ricinoleic acid 35wt% and soybean oil oleic acid 50wt%, under the condition of 18.5 ℃, carry out reverse flotation sorting After the test, the flotation concentrate grade was finally obtained at 65.41%, the flotation tailings product was 22.23%, and the metal recovery rate was 77.54%.

Example 17:

The beneficiation process and pretreatment operation are the same as in Example 1, the iron ore floatation grade is 45.54%, and 3.5 ml of sodium hydroxide aqueous solution, 12.0 ml of starch aqueous solution, 3.0 ml of calcium oxide aqueous solution and 12.3 ml of composite collector aqueous solution are added in sequence , the composite collector contains 35wt% C ₁₆ H ₃₁ COCH(COONa) ₂ , 35wt% ricinoleic acid and 30wt% soybean oilic acid. Under the condition of 18.5 ℃, the reverse flotation separation test of one coarse one fine three sweeps was carried out, and finally the flotation concentrate grade was 67.35%, the flotation tailings product was 23.97%, and the metal recovery rate was 73.54%.

Comparative example 1:

With the iron ore grade, beneficiation process and pretreatment operation of Example 1, add 4.0 milliliters of sodium hydroxide aqueous solution, 13.5 milliliters of starch aqueous solution, 3.5 milliliters of calcium oxide aqueous solution and 11.0 milliliters of KS-III anion collector aqueous solution, in Under the condition of 42°C, a reverse flotation separation test of one coarse, one fine and three sweeps was carried out, and finally the flotation concentrate grade was 66.43%, the flotation tailings grade was 25.24%, and the metal recovery rate was 71.89%.

Comparative example 2:

With the iron ore grade, beneficiation process and pretreatment operation of Example 1, add 4.0 milliliters of sodium hydroxide aqueous solution, 14.0 milliliters of starch aqueous solution, 4.0 milliliters of calcium oxide aqueous solution and 11.0 milliliters of KS-III anion collector aqueous solution, in Under the condition of 42°C, a reverse flotation separation test of one coarse one fine three sweeps was carried out, and finally the grade of flotation concentrate was 65.51%, the grade of flotation tailings was 23.75%, and the metal recovery rate was 75.06%.

Comparative example 3:

With the iron ore grade, beneficiation process and pretreatment operation of Example 1, add 3.5 milliliters of sodium hydroxide aqueous solution, 14.0 milliliters of starch aqueous solution, 4.5 milliliters of calcium oxide aqueous solution and 11.0 milliliters of KS-III anion collector aqueous solution successively, in Under the condition of 43°C, a reverse flotation separation test of one coarse one fine three sweeps was carried out, and finally the grade of flotation concentrate was 65.94%, the grade of flotation tailings was 24.55%, and the metal recovery rate was 73.43%.

Comparative example 4:

With the iron ore grade of embodiment 1, beneficiation process flow and pretreatment operation, add successively 4.0 milliliters of sodium hydroxide aqueous solution, 14.0 milliliters of starch aqueous solution, 4 milliliters of calcium oxide aqueous solution and 12.0 milliliters of industrial oleic acid anion collector aqueous solution, in Under the condition of 42°C, a reverse flotation separation test of one coarse one fine three sweeps was carried out, and finally the grade of flotation concentrate was 66.02%, the grade of flotation tailings was 25.43%, and the metal recovery rate was 71.82%.

Comparative example 5:

With the iron ore grade of embodiment 1, beneficiation process flow and pretreatment operation, add successively 4.0 milliliters of sodium hydroxide aqueous solution, 14.0 milliliters of starch aqueous solution, 3.5 milliliters of calcium oxide aqueous solution and 13.0 milliliters of industrial oleic acid anion collector aqueous solution, in Under the condition of 38°C, a reverse flotation separation test of one coarse, one fine and three sweeps was carried out, and finally the flotation concentrate grade was 65.32%, the flotation tailings grade was 25.15%, and the metal recovery rate was 72.81%.

Experimental research by examples proves that the present invention contains C ₁₆ H ₃₁ COCH(COONa) ₂ , and also contains one or more composite collectors in ricinoleic acid, vegetable oleic acid, animal oleic acid or cottonseed oleic acid, and Compared with the anion collector of the present invention, which only contains C ₁₆ H ₃₁ COCH(COONa) ₂ , for reverse flotation of Anshan type lean hematite at normal temperature, _the cost of purchasing raw materials is lower _. The reduction of the amount of (COONa) ₂ , the improvement and improvement of production index will also be slightly worse. But, under the normal temperature of the embodiment of the present invention, Anshan type poor hematite is carried out to the anion collector of reverse flotation, compared with comparative example KS-III anion collector or industrial oleic acid anion collector, purchase raw material cost similar or slightly lower. The laboratory test results of the separation of lean hematite in Donganshan Sintering Plant have confirmed that normal temperature flotation can be realized, and the temperature of the flotation slurry is reduced from 40-45°C to 17-18°C, with an average decrease of 25°C, and can be significantly reduced. Improve and increase the flotation index, the flotation concentrate grade increased from 66.04% to 66.19%, an increase of 0.15 percentage points; the flotation tailings grade decreased from 25.17% to 23.90%, a decrease of 1.27 percentage points, and the metal recovery rate increased by 2.09 percentage points .

Using the anion collector of the present invention to carry out reverse flotation of Anshan type lean hematite ore under normal temperature, the benefits brought by the improvement and improvement of production index and the benefits brought by the reduction of flotation pulp temperature are calculated as follows:

Dong'anshan Sintering Plant produces 1.95 million tons of concentrate throughout the year, of which flotation concentrate accounts for 55%. The concentrate with iron grade of 65% is priced at 900 yuan per ton, and the grade will increase or decrease by 10 yuan per ton.

①Concentrate grade increased by 0.15 percentage points, annual benefit: 195×0.55×1.5=1.6088 million yuan

②Flotation tailings grade reduced by 1.27 percentage points Annual benefit: Due to the 1.33% increase in flotation concentrate production rate, the annual productive concentrate volume: 195×0.55×1.33%=14264 tons. The price of 66.19% concentrate is 911.9 yuan, 14264×911.9=13.0073 million yuan.

③According to the annual average room temperature of 24°C, the temperature of the slurry drops from 42°C to 24°C, which is a decrease of 18°C. The annual coal saving is 15,800 tons, and the benefit is 15,800×08,000 yuan=12.64 million yuan, and the total benefit is 27.256 million yuan.

Claims (3)

1. the anion collector carrying out reverse flotation to Anshan type lean hematite under normal temperature according to claim 1, is characterized in that, contains C ₁₆ H ₃₁ COCH(COONa) ₂ , Wherein, C ₁₆ H ₃₁ - is a straight-chain alkenyl group having an unsaturated double bond between C _7-8 . 2. the anion collector carrying out reverse flotation to Anshan type lean hematite under normal temperature according to claim 2, is characterized in that, contains C ₁₆ H ₃₁ COCH(COONa) ₂ , also contains ricinoleic acid, vegetable oil one or more of oleic acid, tallow oleic acid or cottonseed oleic acid, Wherein, C ₁₆ H ₃₁ - is a straight-chain alkenyl group having an unsaturated double bond between C _7-8 . 3. according to claim 2 under the normal temperature Anshan type lean hematite is carried out the anion collector of reverse flotation, it is characterized in that, by mass percentage, containing C ₁₆ H ₃₁ COCH (COONa) ₂ is 1 -99%, the rest is one or more of ricinoleic acid, vegetable oleic acid, animal oleic acid or cottonseed oleic acid, Wherein, C ₁₆ H ₃₁ - is a straight-chain alkenyl group having an unsaturated double bond between C _7-8 .