CN106622676B - A kind of mineral flotation foaming agent and its preparation method and application - Google Patents

Abstract

The invention discloses a mineral flotation foaming agent and its preparation method and application. The mineral flotation foaming agent includes modified X oil, C2 _{- C4} fatty alcohol and _C5 -C8 fatty alcohol. _The modified The active components contained in X-ray oil are phosphoric acid ester, cyclohexenyl cyclohexanone, cyclohexyl cyclohexanone and cyclohexyl ether, etc., and its preparation method uses X-oil as raw material to carry out esterification reaction with phosphorus pentachloride in sequence, Carry out hydrolysis reaction with water to obtain modified X oil, and mix modified X oil with C ₂ ~ C ₄ fatty alcohol and C ₅ ~ C ₈ fatty alcohol to obtain mineral flotation foaming agent; the preparation method has wide sources of raw materials, Low cost, simple operation, mild process conditions, the prepared mineral flotation foaming agent is used for mineral flotation, has the advantages of good foaming performance, less dosage, low odor, especially suitable for metal sulfide ore, metal oxide ore or Flotation of non-metallic ores.

Description

A kind of mineral flotation foaming agent and its preparation method and application

technical field

The invention relates to a mineral flotation foaming agent, in particular to a mineral flotation foaming agent prepared by using cyclohexane oxidation by-product X oil, especially suitable for metal sulfide ore, metal oxide ore or non-metallic ore and other minerals The flotation method belongs to the technical field of mineral flotation preparations.

Background technique

In the process of cyclohexane oxidation to cyclohexanone and cyclohexanol, there is a by-product called X oil, and its output accounts for about 5% to 8% of the output of cyclohexanone. Due to the development of my country's nylon chemical fiber industry, the production of cyclohexanone has expanded rapidly, reaching more than 100,000 tons per year, and the output of by-product X oil is large. X-oil appearance is a brown-black viscous liquid, which is mainly burned as fuel at present, and its application range is narrow. There are also some patents on X-oil utilization in China, but relatively few. For example, patent CN104177218A discloses a by-product of cyclohexanone- The method for recovering main components from X oil includes four parts: pretreatment, hydrogenation, hydrolysis and atmospheric-vacuum distillation, and the recovery process is relatively complicated. If the comprehensive utilization of X oil can be realized and the added value of its products can be increased, it will be of great significance no matter from the perspective of environmental protection or economic benefit.

The content of useful components of most mineral resources in the world is relatively low, and mineral resources must be processed to increase the content of useful components for subsequent utilization. Flotation is the most widely used method in the field of mineral resource processing technology. The flotation foaming agent is one of the most important flotation agents in the process of mineral resources processing. In order to effectively separate useful minerals and gangue minerals, it is often necessary to use a foaming agent to generate a large amount of foam and form a large amount of gas-liquid interface to make useful minerals The enrichment floats on the gas-liquid interface and is separated from the gangue. The performance of the foaming agent has a significant impact on the flotation index. Foaming agents are generally polar surface-active substances, which contain polar groups in the molecular structure, which are hydrophilic and enter the liquid phase, such as hydroxyl, carboxyl, ether groups, etc. The other end of the molecule is a non-polar group, which is hydrophilic Enter the gas phase, such as hydrocarbon groups, so that the foaming agent molecules are aligned on the gas-liquid interface. The widely used flotation foaming agent abroad is methyl isobutyl carbinol (MIBC). MIBC is formed by condensation of acetone as raw material. Due to the limitation of current domestic production technology, it is mainly imported, and the price is relatively high, which restricts the application of MIBC in China. There are relatively few types of artificially synthesized foaming agents in my country, and terpineol, a terpineol compound extracted from pine oil, has been used. There are many defects in the terpineol foaming agent. From the perspective of flotation process characteristics, terpineol The generated foam is medium-sized, with less microbubbles, which is not conducive to the attachment of fine-grained ore, and the recovery rate of fine-grained particles is low. At the same time, terpineol has a strong smell and affects human health. The terpineol discharged with tailings has poor biodegradability and pollutes aquatic organisms and the environment.

There have been a lot of reports at home and abroad on the research of new foaming agents. Chinese patent CN1403206A discloses proportioning alcohols with branched chains with ethylene oxide or propylene oxide according to the required ratio, and adding alkali metal K and Na oxides of 0.3% to 1% of the total weight of raw materials as catalysts. The method of reacting in a reaction kettle at a pressure of 0.01-1.2MPa and a temperature of 170-190°C for 2-3 hours, then reducing the pressure to normal pressure, cooling to below 50°C, and filtering to obtain a foaming agent. Chinese patent CN102614994A discloses a method of using monohydric alcohol and polyhydric alcohol as raw materials, reacting in an inert environment at 70-90°C for 1-3 hours under the action of a catalyst, and adjusting the pH value of the product to neutrality to obtain a foaming agent after cooling down to room temperature. Chinese patent CN103721854A discloses a method in which 1-butanol (C ₄ H ₁₀ O) is used as the main flotation foaming agent and tetraethylene glycol (C ₈ H ₁₈ O ₅ ) is used as the auxiliary foaming agent.

So far, terpineol oil and MIBC are still the main foaming agents used in beneficiation production practice. Pinitol oil is derived from natural plants and has complex components. The active ingredient content of common pinitol oil products is only about 50%. However, MIBC is expensive, which is not conducive to popularization and application. Therefore, the modification of X oil and its application in flotation foaming agent is expected to promote the resource utilization of X oil and the development of foaming agent.

Contents of the invention

Aiming at the defects in the prior art, the purpose of the present invention is to provide a mineral flotation foaming agent with good bubble performance, low odor, safety and environmental protection.

Another object of the present invention is to provide a method for preparing the mineral flotation foaming agent with wide source of raw materials, low cost, simple operation and mild process conditions.

The third purpose of the present invention is to provide a mineral flotation foaming agent in mineral flotation, which has the advantages of good foaming performance, less dosage and low odor, and is especially suitable for metal sulfide ores, metal Flotation of oxide ore or non-metallic ore.

In order to achieve the above technical purpose, the present invention provides a mineral flotation foaming agent, comprising the following mass percentage components:

Modified oil 70% ~ 85%;

C ₂ ~C ₄ fatty alcohol 10% ~ 20%;

C ₅ ~C ₈ fatty alcohol 2% ~ 10%;

The mass percent content of each active component in the described modified oil is:

Phosphate 4%~13%;

Cyclohexenyl cyclohexanone 20% to 30%;

Cyclohexyl cyclohexanone 2% to 10%;

Cyclohexyl ether 20% ~ 40%;

Described phosphonate has formula 1 structure:

in,

R ¹ is selected from H, -OH or C ₁ -C ₄ alkyl;

R ² and R ³ are independently selected from —OH or a structural group of formula 2.

In a preferred solution, the C ₂ -C ₄ fatty alcohol is selected from isobutanol.

In a preferred solution, the C ₅ -C ₈ fatty alcohol is selected from iso-octanol.

The present invention also provides a kind of preparation method of described mineral flotation foaming agent, and this method comprises the following steps:

1) Phosphorus pentachloride is esterified with X oil, then hydrolyzed with water, the hydrolysis reaction product is neutralized to neutral, left to stand, oil and water are separated, and the oil layer is modified X oil;

2) The modified X oil is mixed with C ₂ -C ₄ fatty alcohols and C ₅ -C ₈ fatty alcohols to obtain a foaming agent for mineral flotation.

In a preferred scheme, the X oil is an oxidation by-product of cyclohexane, including the following components in mass percentage: 5% to 10% of cyclohexanol derivatives; 20% to 30% of cyclohexenyl cyclohexanone; Hexylcyclohexanone 2% to 10%; cyclohexyl ether 20% to 40%; the balance is cyclohexanone and oligomers.

In a preferred scheme, the conditions of the esterification reaction are as follows: the reaction temperature is 25-60° C., and the reaction time is 1-3 hours.

In a preferred scheme, the conditions of the hydrolysis reaction are as follows: the reaction temperature is 25-60° C., and the reaction time is 1-3 hours.

In a preferred scheme, the mass percent of the phosphorus pentachloride and X oil is 5%-20%: 80%-95%.

In a preferred scheme, the volume ratio of the water to the X oil is 1:3-2:3.

The invention also provides the application of the mineral flotation foaming agent, which is applied to mineral flotation.

In a preferred solution, the mineral is at least one of metal sulfide ore, metal oxide ore, and non-metallic ore.

In a preferred solution, during the flotation process, the amount of the mineral flotation foaming agent relative to the mineral is 10-100 g/t.

The concrete preparation method of mineral flotation foaming agent of the present invention comprises the following steps:

1) Add phosphorus pentachloride to X oil, stir and react at 25-60°C for 1-3 hours, then add water, and hydrolyze at 25-60°C for 1-3 hours to obtain a mixture containing phosphate;

2) Adjust the pH of the product to neutral with an alkaline solution for the phosphate-containing mixture, let it stand until the oil and water are separated, and the oil phase is the modified X oil;

3) Add C ₂ -C ₄ fatty alcohols and C _{5 -C 8} fatty alcohols in sequence to the modified X oil, and mix evenly _. Alcohol 10%~20%, C ₅ ~C ₈ fatty alcohol 2%~10%.

In the flotation foaming agent preparation process of the present invention, the chemical reaction that mainly takes place is as follows:

ROH+PCl ₅ →RCI+POCl ₃ +HCI

The foaming agent includes 3% to 5% of components such as cyclohexanone and oligomers.

In a preferred solution, the alkaline solution includes at least one of sodium hydroxide solution, calcium hydroxide solution, sodium carbonate solution, and saturated sodium bicarbonate solution. Preference is given to saturated sodium bicarbonate solution.

In a preferred scheme, the modified X oil is dehydrated by using anhydrous sodium sulfate, and the amount of anhydrous sodium sulfate is 2-10% relative to the quality of the X oil.

Compared with the prior art, the beneficial technical effect brought by the technical solution of the present invention:

1) The technical solution of the present invention uses cyclohexane oxidation by-product X oil as raw material, X oil is difficult to recycle at present, pollutes the environment, generally uses as fuel, the technical scheme of the present invention will cyclohexane oxidation by-product X oil process simple It can be recycled after treatment, and the mineral flotation foaming agent product with high economic value can be produced, which not only solves the environmental protection problem, but also generates economic value and has a good economic prospect.

2) The technical solution of the present invention has a simple method for preparing a mineral flotation foaming agent and mild process conditions, which is conducive to reducing the energy consumption of the reaction, and is convenient for the control of the reaction process, and does not need to purify the product, which greatly reduces the production cost.

3) The mineral flotation foaming agent prepared by the technical solution of the present invention has low odor, is non-flammable, is safe and environmentally friendly, and has obvious synergistic effect between components, good foaming performance, and small dosage during use, which is especially suitable for It is used in the flotation of minerals such as metal sulfide ore, metal oxide ore or non-metallic ore.

Description of drawings

[Figure 1] is the infrared spectrogram of the phosphate ester in the modified X oil;

[Figure 2] is the nuclear magnetic resonance phosphorus spectrum of phosphate ester in modified X oil;

[Figure 3] is the LC-MS spectrogram of the phosphate ester in the modified X oil;

[Figure 4] is a diagram of the foaming performance test device;

[Fig. 5] is a flow chart of copper sulfide ore flotation process;

[Fig. 6] is a flow chart of the fluorite flotation process;

[Fig. 7] is the flow chart of manganese carbonate ore dressing process.

Detailed ways

The technical solutions of the present invention are described below with specific examples, but the protection scope of the present invention is not limited thereto. Unless otherwise specified, the percentages and parts mentioned in the present invention refer to mass.

The oil used in the following examples is a conventional cyclohexane oxidation by-product, mainly composed of: cyclohexanol derivatives 5% to 10%; cyclohexenyl cyclohexanone 20% to 30%; cyclohexylcyclohexyl Ketone 2% to 10%; cyclohexyl ether 20% to 40%; the balance is cyclohexanone and oligomers.

Example 1

Preparation of modified X oil:

Slowly and uniformly add 15.79 parts of phosphorus pentachloride to 300 parts of X oil, stir and react at 25°C for 1 hour to obtain a mixture. 100 parts of water was added dropwise to the mixture at a constant speed for 10 minutes. After the dropwise addition was completed, the mixture was stirred and reacted at 25° C. for 1 hour to obtain a reaction solution containing phosphate ester. Use saturated aqueous sodium bicarbonate solution to adjust the pH of the reaction solution to neutral, let it stand until the oil and water are separated, take the oil layer and add 15 parts of anhydrous sodium sulfate to dry to obtain the modified X oil. It is calculated that the conversion rate of phosphorus pentachloride is close to 100%, and the selectivity of phosphoric acid ester is 90.3%.

Example 2

Preparation of modified X oil:

Slowly and uniformly add 15.79 parts of phosphorus pentachloride to 300 parts of X oil, stir and react at 25°C for 2 hours to obtain a mixture. 100 parts of water was added dropwise to the mixture at a constant speed for 10 minutes. After the dropwise addition was completed, the mixture was stirred and reacted at 25° C. for 1 hour to obtain a reaction solution containing phosphate ester. Use saturated aqueous sodium bicarbonate solution to adjust the pH of the reaction solution to neutral, let it stand until the oil and water are separated, take the oil layer and add 15 parts of anhydrous sodium sulfate to dry to obtain the modified X oil. It is calculated that the conversion rate of phosphorus pentachloride is close to 100%, and the selectivity of phosphoric acid ester is 92.6%.

Example 3

Preparation of modified X oil:

Slowly and uniformly add 15.79 parts of phosphorus pentachloride to 300 parts of X oil, stir and react at 40°C for 2 hours to obtain a mixture. 100 parts of water was added dropwise to the mixture at a constant speed for 10 minutes. After the dropwise addition was completed, the mixture was stirred and reacted at 25° C. for 1 hour to obtain a reaction solution containing phosphate ester. Use saturated aqueous sodium bicarbonate solution to adjust the pH of the reaction solution to neutral, let it stand until the oil and water are separated, take the oil layer and add 15 parts of anhydrous sodium sulfate to dry to obtain the modified X oil. It is calculated that the conversion rate of phosphorus pentachloride is close to 100%, and the selectivity of phosphate ester is 93.7%.

Example 4

Preparation of modified X oil:

Slowly and uniformly add 15.79 parts of phosphorus pentachloride to 300 parts of X oil, stir and react at 60° C. for 2 hours to obtain a mixture. 100 parts of water was added dropwise to the mixture at a constant speed for 10 minutes. After the dropwise addition was completed, the mixture was stirred and reacted at 25° C. for 1 hour to obtain a reaction solution containing phosphate ester. Use saturated aqueous sodium bicarbonate solution to adjust the pH of the reaction solution to neutral, let it stand until the oil and water are separated, take the oil layer and add 15 parts of anhydrous sodium sulfate to dry to obtain the modified X oil. After calculation, the conversion rate of phosphorus pentachloride is close to 100%, and the selectivity of phosphoric acid ester is 94.8%.

Example 5

Preparation of foaming agent:

Take 8 parts of the modified X-oil obtained in Example (1), 1.5 parts of isobutanol, and 0.5 parts of iso-octanol, add isobutanol and iso-octanol to the modified X-oil in turn, and mix evenly at room temperature to obtain foaming agent.

Example 6

Preparation of foaming agent:

Take 8 parts of the modified X-oil obtained in Example (2), 1 part of isobutanol, and 1 part of iso-octanol, add isobutanol and iso-octanol to the modified X-oil in sequence, and mix evenly at room temperature to obtain foam agent.

Example 7

Preparation of foaming agent:

Take 8 parts of modified X-oil obtained in Example (3), 1.5 parts of isobutanol, and 0.5 parts of iso-octanol, add isobutanol and iso-octanol to the modified X-oil in turn, mix evenly at room temperature to obtain foam agent.

Example 8

Preparation of foaming agent:

Take 8 parts of modified X-oil obtained in Example (4), 1 part of isobutanol, and 1 part of iso-octanol, add isobutanol and iso-octanol to the modified X-oil in turn, mix evenly at room temperature to obtain foam agent.

Example 9

Application of foaming agent in flotation of copper sulfide ore:

In a copper sulfide mine in Yunnan, the copper grade of the raw ore is 0.51%, and the concentration of the grinding slurry is 62.5%. The raw ore is ground to -200 mesh, accounting for 65%, and placed in the flotation tank, and the concentration of the slurry is adjusted to 33%, as follows The dosage is added to the flotation agent: the pH regulator is quicklime, 600g/t; the collector is isobutyl xanthate, 40g/t; the foaming agent is the foaming agent or terpineol oil prepared in Example 5 of the present invention, 22g/t. Carry out a roughing, the flotation process is shown in Figure 5, and the test results are shown in Table 1. As can be seen from the data in the table, the foaming agent prepared in Example 5 is compared with terpineol, and the copper recovery rate in the concentrate has increased by 3.32 percentage points.

Table 1 Flotation test results of copper sulfide ore

Example 10

Application of foaming agent in flotation of fluorite ore:

The CaF ₂ grade of a certain fluorite ore is 38.92%, and the ore is ground to -200 mesh, accounting for 60%. It is placed in a flotation tank. The type and dosage of flotation agents are: pH regulator is sodium carbonate, 1400g/t; Water glass, 400g/t, the collector is sodium oleate, 500g/t, and the foaming agent is the foaming agent or terpineol oil prepared in Example 6 and Example 7 of the present invention, 20g/t. A roughing operation is carried out, and the flotation process flow is shown in Figure 6. Frothing agent among the present invention and pinitol oil flotation comparative experiment result are shown in Table 2. It can be seen from the table that compared with the use of pine alcohol oil as the foaming agent, the recovery of fluorite was increased by 3.15 and 3.36 percentage points respectively when the foaming agents prepared in Example 6 and Example 7 of the present invention were used for flotation.

Table 2 Fluorite flotation test results

Example 11

Application of foaming agent in manganese carbonate ore flotation:

The manganese grade of a low-grade manganese carbonate ore in Guangxi is 7.58%, 80% is ground to -100 mesh, and coarse-grained ore and fine-grained ore are obtained by screening; the coarse-grained ore is subjected to magnetic separation, and the magnetic field strength of the magnetic separation is 1.5T After magnetic separation, magnetic separation concentrate and magnetic separation tailings are obtained. The magnetic separation tailings are reground to -200 mesh, accounting for 80%, and the ground magnetic separation tailings are combined with the fine-grained ores obtained by screening. Enter flotation; after one roughing, two beneficiation and one scavenging, the flotation concentrate and tailings are obtained; the magnetic separation concentrate and the flotation concentrate are combined to obtain the concentrate. The reagents and dosages used in the rough selection are as follows: the collectors are sodium oleate and sodium benzohydroxamate, of which sodium oleate is 1200g/t and sodium benzohydroxamate is 150g/t; the pH regulator is sodium carbonate, adjust The pH value of the pulp is 8; the inhibitor is water glass, 2000g/t; the flocculant is starch, 500g/t; the foaming agent is the foaming agent prepared in Example 8 of the present invention or terpineol oil, 30g/t. In the first beneficiation operation, water glass 500g/t is added, and no chemicals are added for the second beneficiation and sweeping. The beneficiation process flow is shown in Figure 7, and the beneficiation test results are shown in Table 3. It can be seen from the table that compared with the pine oil foaming agent, the foaming agent prepared in Example 8 of the present invention can increase the concentrate recovery rate by 2.69 percentage points and the manganese grade of the concentrate by 0.12 percentage points.

Table 3 Flotation test results of manganese carbonate ore

Claims (10)

1. A mineral flotation frother, characterized in that: comprises the following components in percentage by mass:

70-85% of modified X oil;

C₂～C₄10 to 20 percent of fatty alcohol;

C₅～C₈2 to 10 percent of fatty alcohol;

the modified X oil comprises the following active components in percentage by mass:

4 to 13 percent of phosphonate;

20-30% of cyclohexenyl cyclohexanone;

2 to 10 percent of cyclohexyl cyclohexanone;

20 to 40 percent of cyclohexyl ether;

the phosphonate has the structure of formula 1:

wherein,

R¹selected from H, -OH or C₁～C₄An alkyl group;

R²and R³Independently selected from-OH or a structural group of formula 2.

2. The mineral flotation frother of claim 1, wherein: said C₂～C₄The fatty alcohol is selected from isobutanol; said C₅～C₈The fatty alcohol is selected from isooctyl alcohol.

3. A method of producing a mineral flotation frother as claimed in claim 1 or claim 2, characterised in that: the method comprises the following steps:

1) performing esterification reaction on phosphorus pentachloride and X oil, performing hydrolysis reaction on the phosphorus pentachloride and water, neutralizing a hydrolysis reaction product to be neutral, standing, and performing oil-water layering to obtain an oil layer, namely modified X oil;

2) the modified X oil and C₂～C₄Fatty alcohol and C₅～C₈And mixing the fatty alcohol to obtain the mineral flotation foaming agent.

4. The method of making a mineral flotation frother as recited in claim 3, wherein: the X oil is a cyclohexane oxidation byproduct and comprises the following components in percentage by mass: 5 to 10 percent of cyclohexanol derivatives; 20-30% of cyclohexenyl cyclohexanone; 2 to 10 percent of cyclohexyl cyclohexanone; 20 to 40 percent of cyclohexyl ether; the balance being cyclohexanone and oligomers.

5. The method of making a mineral flotation frother as recited in claim 3, wherein: the esterification reaction conditions are as follows: the reaction temperature is 25-60 ℃, and the reaction time is 1-3 h.

6. The method of making a mineral flotation frother as recited in claim 3, wherein: the conditions of the hydrolysis reaction are as follows: the reaction temperature is 25-60 ℃, and the reaction time is 1-3 h.

7. The method of making a mineral flotation frother as recited in claim 3, wherein:

the mass percentage of the phosphorus pentachloride to the X oil is 5 to 20 percent and 80 to 95 percent;

the volume ratio of the water to the X oil is 1: 3-2: 3.

8. Use of a mineral flotation frother according to claim 1 or 2, wherein: the method is applied to mineral flotation.

9. Use of a mineral flotation frother according to claim 8, wherein: the mineral is at least one of metal sulfide ore, metal oxide ore and non-metal ore.

10. Use of a mineral flotation frother according to claim 9, characterised in that: in the flotation process, the amount of the mineral flotation foaming agent used relative to minerals is 10-100 g/t.