Mineral refining defoaming agent and preparation method thereof

Abstract

The invention relates to a defoaming agent for mineral extraction. The defoaming agent is prepared from the following raw materials in parts by weight: 50-70 parts of a rapid defoaming agent, 10-20 parts of polyether modified fluorosilicone oil, 10-20 parts of polyether, 4-8 parts of fatty alcohol, 5-10 parts of a dispersing agent and 0.1-1 part of a stabilizer. The invention also discloses a preparation method of the mineral refining defoaming agent, which comprises the following specific steps: adding the rapid defoaming agent, the polyether modified fluorosilicone oil and the polyether into a stirring kettle, and stirring until the materials are uniformly mixed; continuously adding the fatty alcohol and the dispersing agent, and continuously stirring for 30-60 minutes at the temperature of 40-80 DEG C until the fatty alcohol and the dispersing agent are uniformly mixed; and finally, adding the stabilizer, and continuously stirring to obtain the defoaming agent. Compared with the prior art, the defoaming agent has the following advantages that the preparation process is simple, foam generated in the mineral refining process in the extreme pH environment is effectively eliminated and inhibited, the performance is stable, the raw materials are cheap, the mineral refining production efficiency can be effectively improved, and huge economic benefits are brought to upstream enterprises.

Description

Technical Field

[0001] The invention belongs to the field of mineral refining and processing, and particularly relates to a mineral refining defoaming agent and a preparation method thereof. Background Art

[0002] In mineral refining, some flotation agents or other surfactants are often added, and there are some impurities in the mineral itself, which will cause a certain amount of foam, occupy the effective volume of the equipment, reduce the processing volume of the slurry, and thus reduce production efficiency; in addition, the foam may lead to incomplete separation of mineral particles, affecting the purity and quality of the final product. A large amount of foam overflowing the equipment will also cause pollution to the operating environment and potential safety hazards. Therefore, it is necessary to add a certain amount of defoaming agent during the mineral refining flotation process. However, the defoaming agents currently used in the mineral refining process on the market have some shortcomings and deficiencies. High-efficiency defoaming agents are usually more expensive, which increases production costs; defoaming agents may contain chemical components that are harmful to the environment and need to be treated after use, which increases environmental protection costs. Some may remain in the slurry, affecting subsequent processes or product quality. In order to overcome these shortcomings, research and development of more efficient, environmentally friendly and low-cost defoaming agents is an important direction at present.

[0003] In the production of alumina, the decomposition process is one of the most important links. In the decomposition process, due to the presence of organic matter in bauxite and external additives, as the organic matter is enriched in the system, a large amount of foam is generated. The presence of a large amount of foam can easily produce a false liquid level, which directly affects production. In the production of wet phosphoric acid, when phosphate rock powder reacts chemically with acid, a large amount of CO2 gas and a considerable amount of HF gas will be released. These gases will overflow the liquid surface with sludge and mineral powder in the viscous reaction liquid. As the acid hydrolysis reaction proceeds violently, the continuously overflowing gas will form a stable foam layer on the surface of the slurry, which directly affects production. Therefore, defoaming agents must be added to eliminate the impact of foam. Since the pH of the decomposition liquid and the extraction liquid is in an extreme environment and has a high temperature in the extraction of the above two minerals, many defoaming agents cannot play a good effect. The commonly used silicone and polyether defoaming agents on the market have poor effects and cannot meet production needs well.

[0004] Therefore, in order to solve one of the above problems, it is necessary to develop a mineral refining defoamer with good defoaming and anti-foaming effects under extreme environments to solve the above problems. Summary of the invention

[0005] In view of the above deficiencies in the prior art, the technical problem to be solved by the present invention is to provide a mineral refining defoaming agent and a preparation method thereof, so as to solve the problems of high production cost, high environmental protection cost and poor defoaming and anti-foaming effect existing in the prior art.

[0006] The present invention solves one of the above technical problems, and the technical solution adopted is: a mineral refining defoamer, which is applied in mineral refining under extreme pH environment, and comprises the following raw materials in parts by weight: 50-70 parts of fast defoaming agent, 10-20 parts of polyether modified fluorosilicone oil, 10-20 parts of polyether, 4-8 parts of fatty alcohol, 5-10 parts of diffusant, and 0.1-1 part of stabilizer.

[0007] Preferably, the rapid defoaming agent is sodium isooctyl sulfosuccinate and its derivatives.

[0008] Preferably, the polyether is one or both of propylene glycol polyether and glycerol polyether.

[0009] Preferably, the polyether is one or both of higher alcohol polyether and glycerol polyether.

[0010] Preferably, the polyether is one or both of hexadecyl-docosapentaenoic alcohol polyether and glycerol polyether (molecular weight 5000-10000).

[0011] Preferably, the fatty alcohol is one or more of ethanol, isopropanol and ethylene glycol.

[0012] Preferably, the fatty alcohol is one or two of n-butanol, n-heptanol, isooctyl alcohol and nonanol.

[0013] Preferably, the fatty alcohol is n-butanol and isooctyl alcohol, and the mass ratio of the two is (0-1):(0-1).

[0014] Preferably, the diffusing agent is one or more of liquid hydrocarbons and aliphatic polyoxyethylene ethers.

[0015] Preferably, the diffusing agent is liquid paraffin or hydrogenated hydrocarbon.

[0016] Preferably, the stabilizer is one or two of sodium carboxymethyl cellulose, polyvinyl alcohol, xanthan gum, and polypropionate.

[0017] Preferably, the mineral refining defoamer can be used for mineral refining under extreme pH environments.

[0018] Preferably, the polyether-modified fluorosilicone oil is of Si-C type.

[0019] Preferably, the preparation steps of the polyether-modified fluorosilicone oil are as follows:

[0020] S1: Add a certain amount of polyether, hydrogen fluoride silicone oil and catalyst into the reaction kettle, stir evenly, stir and heat to 90-150°C, and the reaction time is 4-8h;

[0021] S2: After the reaction in step S1 is completed, the obtained product is cooled to room temperature to obtain a colorless or yellow slightly turbid liquid, which is the polyether-modified fluorosilicone oil.

[0022] Preferably, the polyether in step S1 is one or more of propylene glycol block polyether and double bond polyether.

[0023] Preferably, the catalyst in step S1 is one of chloroplatinic acid-isopropanol solution, platinum-alcohol complex, platinum-alkoxide complex, platinum-ether complex, platinum-ketone complex, and platinum-vinyl complex, and the platinum content of the catalyst in step S1 is 5 to 20 ppm.

[0024] Preferably, the hydrogen-containing fluorosilicone oil in step S1 is low-hydrogen-containing fluorosilicone oil, the hydrogen content of the low-hydrogen-containing fluorosilicone oil is 0.1-0.5wt%, and the fluorine content of the low-hydrogen-containing fluorosilicone oil is 0.1-2wt%.

[0025] Preferably, the hydrogen-containing fluorosilicone oil in step S1 is low-hydrogen-containing fluorosilicone oil, the hydrogen content of the low-hydrogen-containing fluorosilicone oil is 0.1-0.3wt%, and the fluorine content of the low-hydrogen-containing fluorosilicone oil is 0.1-1wt%.

[0026] Preferably, the mass ratio of the polyether to the hydrogen-containing fluorosilicone oil in step S1 is (0-5):(10-30).

[0027] Preferably, the mass ratio of the polyether to the hydrogen-containing fluorosilicone oil in step S1 is (0-2): (15-25)

[0028] The present invention also provides a method for preparing a mineral refining defoamer, comprising the following steps:

[0029] A1: Add the rapid foaming agent, polyether-modified fluorosilicone oil and polyether into a stirring kettle and stir until uniformly mixed. The stirring time is 10 to 30 minutes.

[0030] A2: Add the diffusant and fatty alcohol into a stirring kettle and continue stirring at 40-80°C for 30-60 minutes until uniformly mixed;

[0031] A3: Add the stabilizer into the stirring tank and continue stirring for 10-30 minutes to obtain the defoaming agent.

[0032] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0033] (1) The diffusant and fatty alcohol described in the present invention have stable performance and are almost unaffected by acid and alkali, and can fully exert their defoaming effect. The Si-C polyether modified silicone oil itself has stable performance, but its defoaming power is slightly poor. The introduction of fluorine element further reduces the surface tension and increases its defoaming power and spreadability. In addition, the present invention takes the fast defoaming agent and polyether modified fluorosilicone oil as the core, combined with several other stable defoaming aids, to synergistically exert good defoaming and anti-foaming effects in the process of mineral refining in extreme pH environment. The preparation process is simple, and the raw materials are easily available and cheap, which can effectively improve the production efficiency of mineral refining and bring huge economic benefits to upstream enterprises.

[0034] (2) The harsh environment of mineral refining. Common defoamers on the market include silicones, polyethers, etc., which cannot meet the corresponding defoaming requirements due to their own limitations. Rapid defoamers can quickly penetrate into the surface of the foam to change its surface tension, causing it to lose stability, and work in synergy with other defoaming agents due to their unique diffusion and penetration effects. According to common sense, surfactants, whether anionic or nonionic, have strong foaming and stabilizing effects. The rapid defoamer in the present invention has its foaming and stabilizing effects suppressed under extreme conditions and only plays a defoaming role, which is one of the core points of the present invention. DETAILED DESCRIPTION

[0035] The present invention is further described below by means of specific examples, but is not intended to limit the present invention.

[0036] Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

[0037] Embodiment 1:

[0038] 22 parts of hydrogen-containing fluorosilicone oil (hydrogen content 0.18wt%, fluorine content 0.2wt%) and 1 part of polyether L61 were placed in a reaction kettle, stirred and heated to 120°C, 10ppm chloroplatinic acid-isopropanol solution (calculated as chloroplatinic acid) was added to react for 5h, and cooled to room temperature to obtain a polyether fluorosilicone oil modified product, i.e., polyether modified fluorosilicone oil;

[0039] Add 60 parts of sodium isooctyl sulfosuccinate, 10 parts of polyether modified fluorosilicone oil, and 15 parts of high carbon alcohol polyether into a stirring kettle, and stir for 30 minutes until uniformly mixed; continue to add 3 parts of n-butanol, 3 parts of isooctyl alcohol and 8 parts of liquid paraffin, and continue stirring for 30 minutes at 60°C to make it uniformly mixed; finally, add 0.2 parts of sodium carboxymethyl cellulose, and continue stirring for 15 minutes to obtain a defoaming agent.

[0040] Embodiment 2:

[0041] 15 parts of hydrogen-containing fluorosilicone oil (hydrogen content 0.3wt%, fluorine content 0.5wt%) and 0.8 parts of polyether F6 are placed in a reaction kettle, stirred and heated to 110°C, 10ppm chloroplatinic acid-isopropanol solution (calculated as chloroplatinic acid) is added to react for 6h, and cooled to room temperature to obtain a polyether fluorosilicone oil modified product, i.e., polyether modified fluorosilicone oil;

[0042] 50 parts of sodium isooctyl sulfosuccinate, 20 parts of polyether-modified fluorosilicone oil, and 15 parts of high-carbon alcohol polyether are added into a stirring kettle, and stirred for 30 minutes until uniformly mixed; 3.5 parts of n-butanol, 1.5 parts of isooctyl alcohol, and 10 parts of liquid paraffin are added, and stirred at 60°C for 30 minutes to uniformly mix; finally, 0.2 parts of sodium carboxymethyl cellulose are added, and stirring is continued for 15 minutes to obtain a defoaming agent;

[0043] Embodiment 3:

[0044] 25 parts of hydrogen-containing fluorosilicone oil (hydrogen content 0.1wt%, fluorine content 0.8wt%) and 1.5 parts of propylene glycol block polyether are placed in a reaction kettle, stirred and heated to 100°C, 20ppm chloroplatinic acid-isopropanol solution (calculated as chloroplatinic acid) is added to react for 4h, and cooled to room temperature to obtain a polyether fluorosilicone oil modified product, i.e., polyether modified fluorosilicone oil;

[0045] Add 70 parts of sodium isooctyl sulfosuccinate, 10 parts of polyether modified fluorosilicone oil and 10 parts of glycerol polyether into a stirring kettle and stir for 30 minutes until uniformly mixed; continue to add 2 parts of n-butanol, 2 parts of isooctyl alcohol and 6 parts of liquid paraffin, continue stirring for 30 minutes at 60°C to make it uniformly mixed; finally, add 0.1 parts of sodium carboxymethyl cellulose and 0.1 parts of xanthan gum and continue stirring for 20 minutes to obtain a defoaming agent.

[0046] Embodiment 4:

[0047] 20 parts of hydrogen-containing fluorosilicone oil (hydrogen content 0.2wt%, fluorine content 1wt%) and 1 part of polyether F6 were placed in a reaction kettle, stirred and heated to 100°C, 20ppm chloroplatinic acid-isopropanol solution (calculated as chloroplatinic acid) was added to react for 6h, and cooled to room temperature to obtain a polyether fluorosilicone oil modified product, i.e., polyether modified fluorosilicone oil;

[0048] Add 65 parts of sodium isooctyl sulfosuccinate, 15 parts of polyether modified fluorosilicone oil, and 10 parts of high carbon alcohol polyether into a stirring kettle, and stir for 30 minutes until uniformly mixed; continue to add 2 parts of n-butanol, 2 parts of isooctyl alcohol and 6 parts of liquid paraffin, and continue stirring for 30 minutes at 60°C to make it uniformly mixed; finally, add 0.1 parts of sodium carboxymethyl cellulose and 0.1 parts of xanthan gum, and continue stirring for 20 minutes to obtain a defoaming agent.

[0049] Example 1-Example 4: Polyether L61 is a propylene glycol block polyether L-61 type; Polyether F6 is a chemical substance, and its chemical composition is allyl alcohol polyoxyalkyl ether, which is a non-ionic surfactant and is purchased on the market.

[0050] Example 5: A commercially available silicone polyether defoamer, the main components of which are silicone, silicone polyether, polyether, emulsifier, etc.

[0051] Performance Testing

[0052] The defoaming and antifoaming properties of the defoaming agents in Examples 1-5 were measured. The measurement methods and results are as follows:

[0053] Foaming liquid: decomposition liquid of alumina decomposition tank, phosphoric acid extraction liquid.

[0054] Most mineral refining companies cannot bring out their foaming liquid for confidentiality reasons, so they can only conduct pilot or small-scale tests on site. For example, a Shandong aluminum oxide plant conducted a small-scale test of the circulating bubbling method on site. A southern phosphate fertilizer manufacturer, after replacing phosphate ore with imported phosphate ore from Australia, had severe foaming and conducted a direct pilot test on site.

[0055] 1. Alumina defoaming test:

[0056] Circulation bubbling method (foam suppression effect): clean the circulation bubbling test instrument, add 400mL of decomposition liquid to the circulation bubbling instrument, heat it to 55℃, turn on the air bubbling, wait for the foam volume to rise, record the time and immediately add a certain amount of defoaming agent, record the change of foam volume over time, and record the foam rise time. The longer the time, the better the defoaming effect. The experimental results are shown in Table 1 below.

[0057] Table 1

[0058]

[0059] 2. Phosphate fertilizer defoaming performance test: Add directly to the extraction tank on site to observe the defoaming and anti-foaming effects. The experimental results are shown in Table 2 below.

[0060] Table 2

[0061] sample Defoaming time Anti-foam time Example 1 3min 4.5h Example 4 3.5min 4h Example 5 7min 2h

[0062] In summary: It can be seen from Table 1 and Table 2 that the defoamer obtained by the preparation method described in the scheme of the present invention has good defoaming and anti-foaming effects in the decomposition liquid of the alumina decomposition tank and the phosphate fertilizer extract, and is better than the commercially available silicone polyether defoamer in Example 5.

[0063] The above shows and describes the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

[0064] The matters not described in detail in the present invention are all known technologies to those skilled in the art.

Claims

1. A mineral refining defoamer, characterized in that: The invention comprises the following raw materials in parts by weight: 50-70 parts of a quick defoaming agent, 10-20 parts of polyether-modified fluorosilicone oil, 10-20 parts of polyether, 4-8 parts of fatty alcohol, 5-10 parts of a diffusing agent and 0.1-1 part of a stabilizer.

2. The mineral refining defoamer according to claim 1, characterized in that The rapid foam breaking agent is sodium isooctyl sulfosuccinate.

3. The mineral refining defoamer according to claim 1, characterized in that: The polyether modified fluorosilicone oil is of Si-C type.

4. The mineral refining defoamer according to claim 1, characterized in that The polyether is one or both of higher alcohol polyether and glycerol polyether.

5. The mineral refining defoamer according to claim 1, characterized in that The fatty alcohol is one or more of n-butanol, n-heptanol, isooctyl alcohol and nonanol.

6. The mineral refining defoamer according to claim 1, characterized in that: The stabilizer is one or two of sodium carboxymethyl cellulose, polyvinyl alcohol, xanthan gum and polypropionate.

7. The mineral refining defoamer according to claim 3, characterized in that: The preparation steps of the polyether-modified fluorosilicone oil are as follows: S1: Add a certain amount of polyether, hydrogen fluoride silicone oil and catalyst into the reaction kettle, stir evenly, stir and heat to 90-150°C, and the reaction time is 4-8h; S2: After the reaction in step S1 is completed, the obtained product is cooled to room temperature to obtain a colorless or yellow slightly turbid liquid, which is the polyether-modified fluorosilicone oil.

8. The mineral refining defoamer according to claim 7, characterized in that: The polyether in step S1 is one or more of propylene glycol block polyether and double bond polyether, the catalyst in step S1 is one of chloroplatinic acid-isopropanol solution, platinum-alcohol complex, platinum-alkoxide complex, platinum-ether complex, platinum-ketone complex and platinum-vinyl complex, and the platinum content of the catalyst in step S1 is 5 to 20 ppm.

9. The mineral refining defoamer according to claim 8, characterized in that: The hydrogen-containing fluorosilicone oil in step S1 is low hydrogen-containing fluorosilicone oil, the hydrogen content of the low hydrogen-containing fluorosilicone oil is 0.1-0.3wt%, the fluorine content of the low hydrogen-containing fluorosilicone oil is 0.1-1wt%, and the mass ratio of the polyether to the hydrogen-containing fluorosilicone oil in step S1 is (0-2): (15-25).

10. The method for preparing a mineral refining defoamer according to any one of claims 1 to 9, characterized in that: The steps include: A1: Add the rapid foaming agent, polyether-modified fluorosilicone oil and polyether into a stirring kettle and stir until uniformly mixed. The stirring time is 10 to 30 minutes. A2: Add the diffusant and fatty alcohol into a stirring kettle and continue stirring at 40-80°C for 30-60 minutes until uniformly mixed; A3: Add the stabilizer into the stirring tank and continue stirring for 10-30 minutes to obtain the defoaming agent.

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