Copper smelting acid mist eliminating reagent

Abstract

The invention discloses a copper smelting acid mist eliminating reagent, and relates to the technical field of copper smelting, the reagent is a compound synthesized by taking perfluoroalkyl ethyl alcohol as a raw material, fatty alcohol-polyoxyethylene ether and phosphorus oxychloride, n can be 4 or 6, and represents perfluorobutyl ethyl alcohol and perfluorohexyl ethyl alcohol, and n represents 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 13, 14, 16, 17, 17, 17, 17, 17, 17, 17, 17, 17, 17, 17, 17, 17, 17, 17, 17, 17, 17, 17 m is 6-14 and represents a group of polyoxyethylene ether with the polymerization degree of 6-14, R is C4-C12 fatty alcohol and comprises straight-chain alcohol and branched-chain alcohol, M is an organic matter containing a basic group and is used for neutralizing the acidity of phosphoric acid, one of alanine, arginine, serine, triethanolamine and-amino-2-methyl-1-propanol can be adopted, and n is an integer of 1-3. According to the copper smelting acid mist eliminating reagent, by adopting the reagent provided by the invention, acid mist can be effectively inhibited in a non-ferrous metal electrodeposition process, a relatively good inhibition effect on the acid mist is achieved, and compared with an existing reagent, the reagent has the advantages of being good in acid mist inhibition effect, low in cost and relatively low in price.

Description

Technical Field

[0001] The invention relates to the technical field of copper smelting, in particular to a copper smelting acid mist eliminating agent. Background Art

[0002] Electrolytic processes such as hydrometallurgy will produce acid mist, especially electrolytic copper, because dilute sulfuric acid is used as the electrolyte in the electrolytic cell, the cathode produces oxygen, and the oxygen leaves the liquid surface, and a large amount of acid mist is produced on the liquid surface. Pollute the environment, corrode equipment, and endanger the health of employees. Because the tank surface of the electrolytic workshop must be open, because the metal plate needs to be lifted out of the liquid surface after it is made, the closed method cannot solve the problem. Now some companies use closed covers, which are opened when the metal is discharged, but at this time the acid mist still harms employees and pollutes the environment. Some companies use plastic balls and tarpaulins to cover, but it still cannot solve the problem. Therefore, most of them now use FC1100 to solve the acid mist problem. However, FC1100 is expensive, hundreds of thousands per ton. In order to save costs, some companies have studied the use of conventional surfactants. Some use sodium dodecyl sulfate, and some use soap beans. The use of common surfactants in copper electrowinning, on the one hand, consumes a lot of money and is very expensive, and on the other hand, has a poor effect in suppressing acid mist. In the copper electrowinning extraction process, these surfactants have the effect of emulsifiers. In the copper extraction process, the organic phase is the extractant and the inorganic phase is the aqueous phase. Due to the emulsification effect of the surfactant, the phase separation is poor, the extractant is entrained into the water, and the extractant is lost, resulting in high copper production consumption. In zinc electrowinning, because the consumption of common surfactants is large, some foams are particularly high, and they flash and explode under the action of the current of organic matter on the tank surface, which is very dangerous. The use amount is large, the cost is high, and the foam is serious. The high foam causes the foam between the cathode and the anode to form a conductive layer, short-circuit, reduce the current efficiency, and the foam will overflow the electrolytic cell and pollute the ground. Therefore, a copper smelting acid mist elimination agent is proposed. Summary of the invention

[0003] In view of the deficiencies in the prior art, the present invention provides a copper smelting acid mist eliminating agent, which solves the problems raised in the above background technology.

[0004] To achieve the above purpose, the present invention is implemented by the following technical scheme: a copper smelting acid mist elimination reagent, the reagent is a compound synthesized with perfluoroalkyl ethyl alcohol as a raw material, fatty alcohol polyoxyethylene ether and phosphorus oxychloride, and the chemical formula of the compound is:

[0005]

[0006] Optionally, n may be 4 and 6, representing perfluorobutyl ethyl alcohol and perfluorohexyl ethyl alcohol.

[0007] Optionally, m is 6-14, indicating a polyoxyethylene ether group with a degree of polymerization of 6 to 14.

[0008] Optionally, R is a C4-C12 fatty alcohol, including straight-chain alcohols and branched-chain alcohols.

[0009] Optionally, the M is an organic substance containing a basic group for neutralizing the acidity of phosphoric acid, and may be one of alanine, arginine, serine, triethanolamine, and -amino-2-methyl-1-propanol.

[0010] Optionally, the M contains an amino group and other polar groups such as carboxyl or hydroxyl groups to ensure water solubility.

[0011] The present invention provides a copper smelting acid mist elimination reagent, which has the following beneficial effects:

[0012] The copper smelting acid mist eliminating reagent, by adopting the reagent proposed by the present invention, can effectively suppress the acid mist in the non-ferrous metal electrodeposition process, and has a good suppressing effect on the acid mist. Compared with the existing reagents, the reagent has the advantages of good acid mist suppressing effect, low cost and low price. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 It is a schematic diagram of the structure of the acid mist measuring equipment of the present invention. DETAILED DESCRIPTION

[0014] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0015] See also Figure 1 The present invention provides a technical solution: a copper smelting acid mist elimination reagent, the reagent is a compound synthesized from perfluoroalkyl ethyl alcohol as a raw material, fatty alcohol polyoxyethylene ether and phosphorus oxychloride. The reagent is a liquid and is diluted in water to form a 25% to 50% aqueous solution when used, which is convenient to use. The chemical formula of the compound is:

[0016]

[0017] Here, n can be 4 or 6, which represent perfluorobutyl ethyl alcohol and perfluorohexyl ethyl alcohol.

[0018] Here, m is 6-14, indicating a polyoxyethylene ether group having a polymerization degree of 6 to 14.

[0019] Wherein, R is a C4-C12 fatty alcohol, including straight-chain alcohols and branched-chain alcohols.

[0020] Wherein, M is an organic substance containing a basic group, which is used to neutralize the acidity of phosphoric acid, and can be one of alanine, arginine, serine, triethanolamine, and -amino-2-methyl-1-propanol.

[0021] Among them, M contains amino groups, as well as other polar groups such as carboxyl or hydroxyl groups, which ensure water solubility.

[0022] Manufacturing method of copper smelting acid mist elimination reagent:

[0023] Use a 1000 ml three-necked glass flask, add a certain amount of fatty alcohol polyoxyethylene ether and perfluoroalkyl ethanol, add S phosphorus oxychloride dropwise, heat to 45-100℃ and keep warm for 4-8 hours. Because the reaction between phosphorus oxychloride and fatty alcohol is a classic phosphate synthesis reaction, the reaction is easy to proceed, it is not easy to generate by-products, and it can be carried out in a relatively wide temperature range;

[0024]

[0025] Then add water to hydrolyze, and heat to evaporate the generated hydrochloric acid;

[0026]

[0027] Finally, add glycine arginine or glutamic acid or triethanolamine or alanine, 2-amino-2-methyl-1-propanol for neutralization, and then adjust the pH to 6-8, and add water at the same time to adjust the aqueous solution to the required concentration, and then heat to 40-100℃ for neutralization. Because acid-base neutralization is a relatively easy reaction, the temperature range is wide, and 40-100℃ is a range that can be selected for reference.

[0028] Embodiment 1

[0029] Perfluorobutyl ethanol and Aeo-9 are mixed in a molar ratio of 1:1, wherein AEO-9 is a conventional grade of fatty alcohol polyoxyethylene ether, specifically C11-C13 secondary alcohol polyoxyethylene ether, and the average polymerization degree of polyoxyethylene is 9;

[0030] Aeo-9 (58.2 g, 0.1 mol) and perfluorobutyl alcohol (26.4 g, 0.1 mol) were added to a flask, stirred at room temperature, and phosphorus oxychloride (15.2 g, 0.1 mol) was added dropwise for 30 minutes at 40°C, and kept warm for 12 hours. Water was then added dropwise to allow phosphorus oxychloride to be fully hydrolyzed to generate phosphoric acid diester and hydrochloric acid. The hydrochloric acid was distilled under reduced pressure to fully evaporate the hydrochloric acid in the system;

[0031] Then, triethanolamine (18 g, 0.12 mol) was added, and the mixture was heated to 85° C. and maintained for 2 hours. After the reaction was completed, water was added to adjust the content to 25% to obtain the product.

[0032] Embodiment 2

[0033] Perfluorohexylethanol (36.4 g, 0.1 mol) and Aeo-9 (58.2 g, 0.1 mol) were mixed in a molar ratio of 1:1, wherein AEO-9 is a conventional fatty alcohol polyoxyethylene ether, specifically a C11-C13 secondary alcohol polyoxyethylene ether, and the average degree of polymerization of polyoxyethylene is 9, and then stirred at room temperature, phosphorus oxychloride (15.2 g, 0.1 mol) was added dropwise for 30 minutes;

[0034] Then keep warm at 50°C for 12 hours, then add water dropwise to fully hydrolyze the phosphorus oxychloride to form phosphate diester and hydrochloric acid, distill the hydrochloric acid under reduced pressure, fully evaporate and remove the hydrochloric acid in the system, then add arginine (20.9 g, 0.12 mol), heat to 85°C and keep for 2 hours. After the reaction is completed, add water and adjust the content to 25% to obtain the product.

[0035] Embodiment 3

[0036] Perfluorohexylethanol and Lutensol XP70 were mixed in a molar ratio of 1:1, wherein Lutensol XP70 is a brand of fatty alcohol polyoxyethylene ether produced by BASF, specifically isomeric decanol polyoxyethylene ether, and the average degree of polymerization of polyoxyethylene is 7. Lutensol XP70 (58.2 g, 0.1 mol) and perfluorohexylethanol (36.4 g, 0.1 mol) were added into a flask, stirred at room temperature, and phosphorus oxychloride (15.2 g, 0.1 mol) was added dropwise for 30 minutes;

[0037] Then keep warm at 30°C for 12 hours, then add water dropwise, phosphorus oxychloride is fully hydrolyzed to generate phosphoric acid diester and hydrochloric acid, distill the hydrochloric acid under reduced pressure, evaporate the hydrochloric acid in the system, then add AMP (2-amino-2-methyl-1-propanol) (10.8 g, 0.12 mol), heat to 85°C and keep for 2 hours, the reaction is completed, then add water to adjust the content to 25% to obtain the product.

[0038] Embodiment 4

[0039] Perfluorobutyl ethanol and Lutensol XP70 are mixed in a molar ratio of 1:1, wherein Lutensol XP70 is a brand of fatty alcohol polyoxyethylene ether produced by BASF, specifically isomeric decanol polyoxyethylene ether, and the average polymerization degree of polyoxyethylene is 7;

[0040] Lutensol XP70 (58.2 g, 0.1 mol) and perfluorobutyl alcohol (26.4 g, 0.1 mol) were added into a flask, and then stirred at room temperature, and phosphorus oxychloride (15.2 g, 0.1 mol) was added dropwise for 30 minutes;

[0041] Keep warm at 80°C for 12 hours, then add water dropwise to fully hydrolyze phosphoryl chloride to generate phosphoric acid diester and hydrochloric acid, then distill the hydrochloric acid under reduced pressure to fully evaporate and remove the hydrochloric acid in the system, then add AMP (2-amino-2-methyl-1-propanol) (10.8 g, 0.12 mol), heat to 85°C and keep for 2 hours. After the reaction is completed, add water to adjust the content to 25% to obtain the product.

[0042] You can also continue to combine other reactions to obtain corresponding products;

[0043] Effect verification

[0044] The product prepared in the above embodiment is obtained, and Figure 1 The effect of the sample was verified by the equipment in the apparatus, which consists of an electrolytic cell, a cover, a PP tube, a filter and a vacuum pump. The electrolytic cell is a small 30-liter cell made of fiberglass. The cell is equipped with a silicon rectifier, a cathode plate and an anode plate. A cover is provided at the top of the electrolytic cell, which is covered by the cover. A through hole is provided on the surface of the cover. The through hole leads the gas out through a DN50 PP pipe. The gas passes through the PP plastic tube and enters the filter made of PP material. The diameter of the filter is DN80. A number of meshes are provided at the bottom of the filter. The surface of the meshes is covered with a filter membrane. The outlet of the filter is connected to the vacuum pump.

[0045] The method of using the equipment is as follows: add the configured copper sulfate and dilute sulfuric acid solution to the electrolytic cell, connect the silicon rectifier to the power supply, the system starts working, then cover the cover and lock it with a buckle, start the vacuum pump, and extract the acid mist in the system. The vacuum pump and the system are configured with a regulating valve to control the vacuum degree in the electrolytic cell and maintain a slight negative pressure in the system. The electrolytic cell continuously generates acid mist, which enters the filter through the pipeline connected to the cover. The filter membrane of the filter is a microporous filter membrane with very small holes, which can filter out the acid mist and allow the gas to pass through. The filter membrane is generally made of PVDF. After a certain period of time, the power supply is terminated, the filter membrane is taken out, the filter membrane and the filter are rinsed with water, the rinse water is collected, and the rinse water is titrated with a potassium hydroxide standard solution. According to the consumption of the standard solution, the amount of sulfuric acid in the filter is calculated, and the release amount of sulfuric acid mist is obtained. In the sulfuric acid solution, no additives are added, and the amount of sulfuric acid obtained after electrolytic deposition for a certain period of time is the reference amount M. After adding the acid mist inhibitor, the amount of acid mist obtained is recorded as the comparison amount m, so (Mm) / M is obtained, which is the acid mist suppression efficiency.

[0046] Verification Example 1

[0047] Add the prepared copper sulfate and sulfuric acid mixture into the acid mist measuring equipment. Turn on the power supply for 30 minutes, collect the sulfuric acid mist, and then titrate it to calculate the consumption of 22.1 g of 1 mol / L potassium hydroxide.

[0048] Verification Example 2

[0049] The components of Example 1 were added to the copper sulfate solution at a concentration of 1 part per 100,000, and the power was turned on for 30 minutes. The sulfuric acid mist was collected and titrated. The consumption of 0.7 g of 1 mol / L potassium hydroxide was calculated, and the acid mist inhibitor efficiency was 96.8%.

[0050] Verification Example 3

[0051] The components of Example 1 were added to the copper sulfate solution at a concentration of 1 part per 100,000, and the power was turned on for 30 minutes. The sulfuric acid mist was collected and titrated. The consumption of 0.66 g of 1 mol / L potassium hydroxide was calculated, and the acid mist inhibitor efficiency was 97%.

[0052] Verification Example 4

[0053] The components of Example 2 were added to the copper sulfate solution at a concentration of 1 part per 100,000, and the power was turned on for 30 minutes. The sulfuric acid mist was collected and titrated. The consumption of 0.77 g of 1 mol / L potassium hydroxide was calculated, and the acid mist inhibitor efficiency was 96.5%.

[0054] Verification Example 5

[0055] The components of Example 3 were added to the copper sulfate solution at a concentration of 1 part per 100,000, and the power was turned on for 30 minutes. The sulfuric acid mist was collected and titrated. The consumption of 1.1 g of 1 mol / L potassium hydroxide was calculated, and the acid mist inhibitor efficiency was 95%.

[0056] Verification Example 6

[0057] The acid mist suppressant efficiency was calculated consuming 1.22 g of 1 mol / L potassium hydroxide.

[0058] Verification Example 7

[0059] Calculate the acid mist suppressant efficiency consuming 1.25 g of 1 mol / L potassium hydroxide.

[0060] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A copper smelting acid mist elimination reagent, characterized in that: The reagent is a compound synthesized from perfluoroalkylethyl alcohol as a raw material, fatty alcohol polyoxyethylene ether and phosphorus oxychloride, and the chemical formula of the compound is:

2. A copper smelting acid mist elimination reagent according to claim 1, characterized in that: The n may be 4 or 6, which represent perfluorobutyl ethyl alcohol and perfluorohexyl ethyl alcohol.

3. A copper smelting acid mist elimination reagent according to claim 1, characterized in that: The m being 6-14 indicates a polyoxyethylene ether group having a polymerization degree of 6 to 14.

4. A copper smelting acid mist elimination reagent according to claim 1, characterized in that: The R is a C4-C12 fatty alcohol, including straight-chain alcohols and branched-chain alcohols.

5. A copper smelting acid mist elimination reagent according to claim 1, characterized in that: The M is an organic substance containing a basic group, which is used to neutralize the acidity of phosphoric acid, and can be one of alanine, arginine, serine, triethanolamine, and -amino-2-methyl-1-propanol.

6. A copper smelting acid mist elimination reagent according to claim 1, characterized in that: The M contains an amino group and other polar groups such as a carboxyl group or a hydroxyl group, thereby ensuring water solubility.

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