W / O emulsion collector for electrolytic aluminum and preparation and application thereof

Abstract

The present application belongs to the field of carbon residue resource utilization, and relates to a W / O emulsion collector for electrolytic aluminum and a preparation and application thereof. The present application adopts kerosene as an external phase, a KCl solution as an internal phase, and an alkyl glycoside (or polyisobutylene ethanolamine) as an emulsifier to prepare a high internal phase W / O emulsion collector, and the high internal phase W / O emulsion collector is used in a flotation decarburization and upgrading process of electrolytic aluminum carbon residue, so that the carbon resource in the carbon residue can be efficiently removed under the condition of low oil consumption, the content of carbon impurities in the cosolvent is reduced, the cosolvent can be recycled and reused in the electrolytic aluminum process, and the present application is of great significance to the sustainable development of the electrolytic aluminum industry and the resource utilization of the carbon residue, and has a good application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of carbon residue resource utilization, and particularly relates to a W / O emulsion collector for electrolytic aluminum and a preparation and application thereof. BACKGROUND

[0002] In the process of electrolytic aluminum, both the cathode and the anode are carbon-containing materials. Due to electrochemical reaction and electrolyte immersion, the carbon materials of the cathode and the anode are consumed, peeled off, broken, etc., and a large amount of carbon residue is generated. The carbon residue is mixed with the necessary electrolyte solvent, resulting in a decrease in the efficiency of the electrolyte solvent, and finally, a carbon-containing solid waste is generated. At the same time, the solid waste is also mixed with the salt in the electrolyte, and can only be discarded as hazardous waste, resulting in resource waste and an increase in processing cost.

[0003] An important step for realizing resource utilization of the carbon-containing solid waste of electrolytic aluminum is to separate the carbon from the electrolyte solvent, and the main method for separation is flotation. Diesel is commonly used as a collector and No. 2 oil is used as a foaming agent for decarburization by flotation, but the flotation efficiency is poor. Patent CN112844852A discloses a mixed collector for decarburization of carbon-containing solid waste of electrolytic aluminum, which is prepared from hydrocarbon oil, lipid oil and phthalate ester, etc. Although the flotation effect is improved, the oil consumption is large, and the treatment effect on fine particle carbon-containing solid waste is poor. The obtained electrolyte solvent still has a high carbon impurity content, and is difficult to be recycled. SUMMARY

[0004] The purpose of the present application is to provide a W / O emulsion collector for electrolytic aluminum and a preparation and application thereof, which focuses on resource utilization of high-carbon waste residue, and solves the technical problems of large oil consumption, poor flotation efficiency and difficulty in recycling the electrolyte solvent in the existing decarburization process by flotation. The separated carbon can be used as a raw material to prepare high-value carbon materials, and the electrolyte solvent can be recycled.

[0005] To achieve the above purpose, the present application is realized by the following technical scheme:

[0006] In one aspect, the present application provides a preparation method of a W / O emulsion collector for electrolytic aluminum, which comprises the following steps:

[0007] Step 1: Kerosene is added to alkyl polyglycoside or polyisobutylene ethanolamine, and stirred to obtain liquid product A;

[0008] Step 2: KCl solution is added to the liquid product A, and the stirring is continued to obtain the W / O emulsion collector.

[0009] In the above technical scheme, kerosene is used as the external phase, KCl solution is used as the internal phase, and alkyl polyglycoside (or polyisobutylene ethanolamine) is used as the emulsifier, so as to prepare a high internal phase W / O emulsion collector. The emulsifier used is green and degradable, the volume ratio of the water phase in the obtained emulsion is high, the size distribution of the emulsion droplets is uniform, and the stability is strong.

[0010] Preferably, the mass ratio of kerosene to alkyl polyglycoside or polyisobutylene ethanolamine in step 1 is 5:1 to 3:1.

[0011] Preferably, the stirring speed in step 1 is 1000 to 2000 r / min, and the stirring time is 5 to 10 min.

[0012] Preferably, the mass concentration of KCl solution in step 2 is 6 to 7%, and the volume ratio of KCl solution to liquid product A is 4:1 to 6:1.

[0013] Preferably, the KCl solution is added to the liquid product A at a uniform speed of 2 to 4 mL / min in step 2, and continuous stirring is carried out during the addition process at a stirring speed of 1100 to 2000 r / min to prevent phase inversion of the emulsion.

[0014] Preferably, the stirring speed in step 2 is 8000 to 10000 r / min, and the stirring time is 10 to 15 min to make the particle size of the emulsion collector uniform.

[0015] Another aspect of the present application provides a W / O emulsion collector prepared by the above method.

[0016] Another aspect of the present application also provides the application of the above W / O emulsion collector in the separation of electrolytic aluminum carbon-containing solid waste, which specifically comprises the following steps:

[0017] Step 1: adding electrolytic aluminum carbon residue into water and stirring to obtain a mixed liquid B;

[0018] Step 2: adding the W / O emulsion collector into the mixed liquid B and stirring to obtain a mixed liquid C;

[0019] Step 3: then adding a foaming agent into the mixed liquid C, introducing air for flotation separation, and scraping foam to obtain carbon material.

[0020] Preferably, the solid-liquid mass ratio of electrolytic aluminum carbon residue to water in step 1 is 1:20 to 1:25, and the mass ratio of the W / O emulsion collector to the mixed liquid B in step 2 is 1:33000 to 1:34000, the stirring speed is 1000 to 1200 r / min, and the stirring time is 2 to 3 min.

[0021] Preferably, the foaming agent in step 3 is secondary octanol, the addition amount of secondary octanol is 0.4 to 0.5 times the addition amount of the W / O emulsion collector, the flotation separation conditions are as follows: continuously stirring at a speed of 1000 to 1200 r / min, controlling the gas flow to be 10 to 15 mL / min, and scraping foam at a time interval of 10 to 15 s.

[0022] Compared with the prior art, the present application has the following advantages:

[0023] The W / O emulsion collector provided by the present application can realize efficient removal and recovery of carbon resources in electrolytic aluminum carbon residue by flotation method (the flotation recovery rate of carbon reaches 80-85%) under a low dosage, while greatly reducing the content of carbon impurities in the cosolvent, and has the advantages of simple process, high efficiency and the like. The carbon obtained by flotation separation can be used for preparation of high-value carbon materials, and the cosolvent can be recycled and reused in the electrolytic aluminum process, which has very important significance for sustainable development of the electrolytic aluminum industry and resource utilization of carbon residue. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 It is a microscope picture of the W / O emulsion collector of the present application. DETAILED DESCRIPTION

[0025] In order to facilitate understanding of the present application, the present application will be described in more detail below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application.

[0026] Example 1

[0027] Preparation of the W / O emulsion collector

[0028] Step 1: 6.25g of kerosene was added to 1.25g of alkyl polyglycoside, and stirred at a speed of 1000r / min for 5min to obtain liquid product A;

[0029] Step 2: 35g of KCl solution with a mass concentration of 6% was added to liquid product A at a uniform speed of 2mL / min through a flowmeter, and the stirring was continued at a speed of 1100r / min during the adding process until the addition of KCl solution was completed, to obtain liquid product B;

[0030] Step 3: liquid product B was moved to a high-speed stirrer, and stirred at a speed of 8000r / min for 10min to obtain the W / O emulsion collector. The type of emulsion was determined by dilution dispersion method and fluorescence staining method, and the size of emulsion was determined by optical microscope and dynamic light scattering, and the size of emulsion droplets was mainly distributed in 10-40μm.

[0031] Application of the W / O emulsion collector

[0032] Step 1: 5g of electrolytic aluminum carbon residue was added to 100mL of water and stirred and dispersed for 5min to make the carbon residue sample fully wetted, to obtain a mixture D;

[0033] Step 2: 3.1 mg of the W / O emulsion collector prepared in the above method was added into the mixed solution D, and stirring was continued at a stirring speed of 1000 r / min for 2 min to obtain a mixed solution E;

[0034] Step 3: The mixed solution E was transferred into a flotation tube, 1.24 mg of sec-octyl alcohol was added into the flotation tube as a foaming agent, and stirring was continued at a stirring speed of 1000 r / min, air was introduced from the bottom of the flotation tube at a gas flow rate of 10 mL / min, and flotation was carried out for 5 min, the foam floated to the top of the flotation tube was scraped out at an interval of 10 s, and then filtration, washing, drying and recovery were carried out to obtain a carbon product, and the flotation yield of the carbon was 80%.

[0035] Step 4: The product remaining in the flotation tube was subjected to filtration, washing, drying and recovery to obtain a co-solvent for electrolytic aluminum, and the recovery rate of the co-solvent was 88%.

[0036] Example 2

[0037] Preparation of the W / O emulsion collector

[0038] Step 1: 4.5 g of kerosene was added into 1.5 g of polyisobutylene ethanolamine (PIB), and stirring was carried out at a stirring speed of 1100 r / min for 6 min to obtain a liquid product A;

[0039] Step 2: 40 g of a KCl solution with a mass concentration of 6% was added into the liquid product A at a constant speed of 3 mL / min through a flowmeter, and stirring was continued at a stirring speed of 1200 r / min during the addition until the addition of the KCl solution was completed to obtain a liquid product B;

[0040] Step 3: The liquid product B was transferred into a high-speed stirrer, and stirring was carried out at a stirring speed of 9000 r / min for 12 min to obtain a W / O emulsion collector, the type of the emulsion was determined by a dilution dispersion method and a fluorescent staining method, the size of the emulsion was determined by an optical microscope and dynamic light scattering, and the size of the emulsion droplets was mainly distributed in a range of 20-40 μm.

[0041] Application of the W / O emulsion collector

[0042] Step 1: 6 g of carbon residue of electrolytic aluminum was added into 130 mL of water, and stirring and dispersion were carried out for 6 min to make the carbon residue sample fully wetted to obtain a mixed solution D;

[0043] Step 2: 4.1 mg of the W / O emulsion collector prepared in the above method was added into the mixed solution D, and stirring was continued at a stirring speed of 1100 r / min for 2 min to obtain a mixed solution E;

[0044] Step 3: Transfer the mixture E to the flotation tube, add 1.85 mg of sec-octyl alcohol as a foaming agent, continue stirring at a stirring speed of 1100 r / min, introduce air from the bottom of the flotation tube, control the gas flow at 12 mL / min, float for 8 min, scrape the foam floated to the top of the flotation tube at a time interval of 12 s, perform suction filtration, washing, drying, and recovery, to obtain the carbon product, and the flotation yield of carbon is 82%;

[0045] Step 4: Perform suction filtration, washing, drying, and recovery on the product remaining in the flotation tube, to obtain the electrolytic aluminum co-solvent, and the recovery rate of the co-solvent is 90%.

[0046] Example 3

[0047] Preparation of W / O emulsion collector

[0048] Step 1: Add 8 g of kerosene to 2 g of alkyl polyglycoside, and stir at a stirring speed of 1500 r / min for 8 min to obtain liquid product A;

[0049] Step 2: Add 70 g of a KCl solution with a mass concentration of 7% to liquid product A at a uniform speed of 4 mL / min through a flowmeter, and stir at a stirring speed of 1800 r / min during the addition until the addition of the KCl solution is completed, to obtain liquid product B;

[0050] Step 3: Move liquid product B to a high-speed stirrer, and stir at a speed of 9000 r / min for 14 min to obtain the W / O emulsion collector, the type of the emulsion is determined by the dilution dispersion method and fluorescent staining method, and the size of the emulsion is determined by optical microscopy and dynamic light scattering, and the size of the emulsion droplets is mainly distributed in the range of 10-40 μm.

[0051] Application of W / O emulsion collector

[0052] Step 1: Add 8 g of electrolytic aluminum carbon residue to 185 mL of ultrapure water, and stir and disperse for 8 min to fully wet the carbon residue sample, to obtain mixture D;

[0053] Step 2: Add 5.8 mg of the W / O emulsion collector prepared by the above method to mixture D, and continue stirring at a stirring speed of 1200 r / min for 3 min to obtain mixture E;

[0054] Step 3: Transfer mixture E to the flotation tube, add 2.9 mg of sec-octyl alcohol as a foaming agent, continue stirring at a stirring speed of 1200 r / min, introduce air from the bottom of the flotation tube, control the gas flow at 14 mL / min, float for 6 min, scrape the foam floated to the top of the flotation tube at a time interval of 14 s, perform suction filtration, washing, drying, and recovery, to obtain the carbon product, and the flotation yield of carbon is 85%.

[0055] Step 4: The product remaining in the flotation tube is filtered, washed, dried and recovered to obtain the flux for electrolytic aluminum. The recovery rate of the flux is 93%.

[0056] Example 4

[0057] Preparation of W / O type emulsion collectors

[0058] Step 1: Add 10g of kerosene to 2.5g of polyisobutylene ethanolamine and stir at 2000r / min for 10min to obtain liquid product A;

[0059] Step 2: Add 100g of 6% KCl solution dropwise to liquid product A at a rate of 4mL / min using a flow meter. During the dropwise addition, continue stirring at a rate of 2000r / min until the addition of KCl solution is completed, to obtain liquid product B.

[0060] Step 3: Transfer liquid product B to a high-speed mixer and stir at 10000 r / min for 15 min to obtain a W / O type emulsion collector. The emulsion type is determined by dilution dispersion method and fluorescence staining method. The emulsion size is measured by optical microscopy and dynamic light scattering. The emulsion droplet size is mainly distributed in 10-30 μm.

[0061] Application of W / O type emulsion collectors

[0062] Step 1: Add 10g of electrolytic aluminum carbon slag to 250mL of ultrapure water and stir for 10min to fully wet the carbon slag sample to obtain mixture D;

[0063] Step 2: Add 7.9 mg of the W / O emulsion collector prepared by the above method to mixture D, and continue stirring at 1200 r / min for 3 min to obtain mixture E;

[0064] Step 3: Transfer the mixture E to the flotation tube, add 3.95 mg of 2-octanol as a frother, stir continuously at 1200 r / min, introduce air from the bottom of the flotation tube at a flow rate of 15 mL / min, float for 5 min, scrape off the foam that rises to the top of the flotation tube at 15 s intervals, filter, wash, dry, and recover to obtain the carbon product. The carbon flotation yield is 83%.

[0065] Step 4: The product remaining in the flotation tube is filtered, washed, dried, and recovered to obtain the flux for electrolytic aluminum. The recovery rate of the flux is 89%.

[0066] Any combination of the technical features in the above-described embodiments can be made, and for the sake of brevity, not all possible combinations are described, however, as long as the combination of the technical features does not exist in contradiction, it shall be considered within the scope of the present disclosure.

[0067] The above-described embodiments only express several implementation manners of the present application, and the description is relatively specific and detailed, but it shall not be understood as a limitation on the patent scope of the present application. It shall be pointed out that, for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, and these shall be within the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the appended claims.

Claims

1. A method for preparing a W / O type emulsion collector for separating carbon-containing solid waste from electrolytic aluminum, characterized in that: Includes the following steps: Step 1: Add kerosene to alkyl glycoside or polyisobutylene ethanolamine, stir, and obtain liquid product A; Step 2: Add KCl solution to liquid product A and continue stirring to obtain the W / O type emulsion collector; In step 1, the mass ratio of kerosene to alkyl glycoside or polyisobutylene ethanolamine is 5:1 to 3:

1. In step 2, the mass concentration of the KCl solution is 6-7%; the volume ratio of the KCl solution to liquid product A is 4:1 to 6:

1.

2. The method for preparing a W / O type emulsion collector for separating carbon-containing solid waste from electrolytic aluminum, as described in claim 1, is characterized in that: In step 1, the stirring speed is 1000-2000 r / min and the stirring time is 5-10 min.

3. The method for preparing a W / O type emulsion collector for separating carbon-containing solid waste from electrolytic aluminum, as described in claim 1, is characterized in that: In step 2, the KCl solution is added dropwise to liquid product A at a rate of 2-4 mL / min, and continuous stirring is carried out during the dropwise addition process at a stirring speed of 1100-2000 r / min.

4. The method for preparing a W / O type emulsion collector for separating carbon-containing solid waste from electrolytic aluminum, as described in claim 1, is characterized in that: In step 2, the stirring speed is 8000-10000 r / min and the stirring time is 10-15 min.

5. A W / O emulsion collector prepared by the method according to any one of claims 1 to 4.

6. The application of a W / O emulsion collector prepared by the method of any one of claims 1 to 4 or the W / O emulsion collector of claim 5 in the separation of carbon-containing solid waste from electrolytic aluminum, characterized in that: Includes the following steps: Step 1: Add the electrolytic aluminum carbon slag to water and stir to obtain mixture B; Step 2: Add the W / O type emulsion collector to mixture B, stir, and obtain mixture C; Step 3: Then add a foaming agent to the mixture C, introduce air for flotation separation, and scrape off the foam to obtain carbonaceous material.

7. The application of the W / O type emulsion collector according to claim 6, characterized in that: In step 1, the solid-liquid mass ratio of electrolytic aluminum carbon slag to water is 1:20 to 1:25; in step 2, the mass ratio of W / O type emulsion collector to mixture B is 1:33000 to 1:34000, the stirring speed is 1000 to 1200 r / min, and the stirring time is 2 to 3 min.

8. The application of the W / O type emulsion collector according to claim 6, characterized in that: The flotation separation conditions are as follows: the frother in step 3 is 2-octanol, and the amount of 2-octanol added is 0.4 to 0.5 times the amount of W / O type emulsion collector added. The flotation separation conditions are as follows: continuous stirring at a speed of 1000 to 1200 r / min, gas flow rate controlled at 10 to 15 mL / min, flotation time of 5 to 8 min, and skimming of bubbles at a time interval of 10 to 15 s.

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