CN111217356A - Method for recovering porous carbon from aluminum electrolysis anode carbon slag - Google Patents
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Abstract
The invention discloses a method for recovering porous carbon from aluminum electrolysis anode carbon slag, which comprises the following steps: (1) uniformly mixing aluminum electrolysis anode carbon residue, concentrated sulfuric acid and an oxidant according to the mass ratio of 1: 0.2-10: 0-5 to obtain a mixture A, and placing the mixture A at 100-300 ℃ for primary roasting to obtain a primary roasted product; (2) washing, filtering and drying the primary roasting product to obtain a product B, uniformly mixing the product B and an activating agent according to the mass ratio of 1: 1-10 to obtain a mixture C, and roasting the mixture C at 300-1500 ℃ for the second time to obtain a secondary roasting product; (3) and washing, filtering and drying the secondary roasting product to obtain the porous carbon material. The method does not generate high-temperature fluorine-containing flue gas and fluorine-containing wastewater in the treatment process, and can recover fluorine and aluminum elements to obtain the high-purity porous carbon material, thereby realizing the comprehensive recovery and cleaning treatment of the aluminum electrolysis anode carbon residue.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of solid waste in electrolytic aluminum industry, and particularly relates to a method for recovering porous carbon from aluminum electrolysis anode carbon slag.
Background
In the production process of aluminum, due to uneven combustion, selective oxidation, erosion and scouring of aluminum liquid and electrolyte and the like of a carbon anode, part of carbon particles fall off from the anode and enter molten salt electrolyte, so that anode carbon slag is generated. Due to the difference between the anode quality and the electrolysis process, about 9kg of anode carbon residue is generated when 1t of aluminum is produced, the yield of raw aluminum in China reaches 3580 ten thousand tons in 2019, more than 30 ten thousand tons of anode carbon residue are generated, and the quantity is huge. The main components of the anode carbon residue are carbon, cryolite, sodium fluoride, calcium fluoride, aluminum oxide and the like, and the anode carbon residue belongs to hazardous waste. If the piles are piled in the open air, soluble fluoride such as sodium fluoride in the piles can permeate into the ground along with rainwater to pollute the ground water, thereby causing great harm to organisms and environment.
At present, the recovery mode of the aluminum electrolysis anode carbon slag can be summarized into two recovery processes, namely a pyrogenic process taking a high-temperature roasting method and a vacuum smelting method as the core and a wet process mainly taking flotation. The high-temperature roasting method uses carbon in the aluminum electrolysis anode carbon residue as fuel for combustion, a large amount of fluoride can volatilize at high temperature (1000 ℃) in the process, serious corrosion is caused to subsequent flue gas treatment equipment, and the method can not recover the carbon material in the carbon residue. The electrolyte which can be directly returned to the aluminum electrolysis production can be obtained by processing the aluminum electrolysis carbon slag by a vacuum smelting method, but the carbon content of the residual carbon component is only 74 percent, so that the problem that secondary carbon powder is difficult to process is faced. The electrolyte obtained by processing the anode carbon residue by the flotation method contains about 5 percent of carbon, the obtained carbon powder contains about 9 percent of electrolyte, the carbon powder is difficult to directly return to an aluminum electrolysis system, and a large amount of fluorine-containing wastewater is generated in the process and is difficult to process.
Disclosure of Invention
The invention aims to provide a method for recovering porous carbon from aluminum electrolysis anode carbon slag, aiming at the problems that in the prior art, a large amount of fluoride generated in the recovery process of the aluminum electrolysis anode carbon slag volatilizes at high temperature (1000 ℃), the subsequent flue gas treatment equipment is seriously corroded, the prepared carbon material has high impurity content, and a large amount of fluorine-containing wastewater is generated and is difficult to treat.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for recovering porous carbon from aluminum electrolysis anode carbon slag, which comprises the following steps:
(1) uniformly mixing aluminum electrolysis anode carbon residue, concentrated sulfuric acid and an oxidant according to the mass ratio of 1: 0.2-10: 0-5 to obtain a mixture A, and placing the mixture A at 100-300 ℃ for primary roasting to obtain a primary roasted product;
(2) washing, filtering and drying the primary roasting product to obtain a product B, uniformly mixing the product B and an activating agent according to the mass ratio of 1: 1-10 to obtain a mixture C, and roasting the mixture C at 300-1500 ℃ for the second time to obtain a secondary roasting product;
(3) and washing, filtering and drying the secondary roasting product to obtain the porous carbon material.
In a preferred scheme, the grain size of the aluminum electrolysis anode carbon slag is less than 0.50mm, and the carbon content is more than 35%.
In a preferable scheme, the concentration of the concentrated sulfuric acid is 15.0-18.4 mol/L.
More preferably, the concentration of the concentrated sulfuric acid is 17.0-18.4 mol/L.
In a preferred embodiment, the oxidizing agent is at least one of cobalt trifluoride, sodium persulfate, potassium monopersulfate, ammonium persulfate, hydrogen peroxide, potassium dichromate, sodium dichromate, ammonium dichromate, potassium ferrate, potassium permanganate, sodium permanganate, ammonium permanganate, calcium permanganate, zinc permanganate, magnesium permanganate, potassium periodate, sodium periodate, potassium perchlorate, sodium perchlorate, potassium chlorate, sodium chlorate, magnesium chlorate, potassium nitrate, sodium nitrate, ammonium nitrate, and nitric acid.
In a preferred scheme, the mass ratio of the aluminum electrolysis anode carbon residue to the concentrated sulfuric acid to the oxidant is 1: 0.5-5: 0-2.
Preferably, in the step (1), the mixture A is placed at 150-250 ℃ for primary roasting.
In the preferable scheme, in the step (1), the primary roasting time is 0.1-10 hours; more preferably, the primary roasting time is 1.0-5.0 hours.
In the present invention, the primary firing aims to: sulfuric acid is used for reacting with non-carbon components in the aluminum electrolysis anode carbon residue to remove fluorine elements and convert part of insoluble substances in the aluminum electrolysis anode carbon residue into soluble substances, so that the generation of high-fluorine wastewater can be avoided and the purification of the carbon residue is facilitated; and (3) introducing functional groups on the carbon material by using a concentrated sulfuric acid solution with oxidability and an oxidant so as to be beneficial to the subsequent activated pore-forming. The main reactions of the non-carbon components in the process are:
[NaF+AlF3+CaF2+Na3AlF6]+H2SO4→HF(g)+CaSO4+nNa2SO4·Al2(SO4)3(1)
nMeO·SiO2+H2SO4+NaF→Mem·(SO4)+SiF4(g)(2)
nMeO·Al2O3+H2SO4→Mem·(SO4)(3)
under oxidizing conditions, the carbon material can be transformed as follows:
-C-→-COOH+-COH+-CH2-(4)
in the preferable scheme, in the step (1), the flue gas generated by primary roasting is absorbed and recovered by an alumina dry method.
Preferably, in the step (2), the mass ratio of the product B to the activating agent is 1: 3-7.
In a preferred embodiment, the activating agent is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium chloride, and potassium chloride.
Preferably, in the step (2), the mixture C is subjected to secondary roasting at 500-1000 ℃.
In the preferable scheme, in the step (2), the secondary roasting time is 0.1-20 hours; in a more preferable scheme, the secondary roasting time is 1.0-10 hours.
In the present invention, the secondary baking is aimed at: reacting an activating agent with a carbon material to form pores; the remaining insoluble non-char components (mainly alumina, silica, aluminosilicates) are converted to solubles by means of an activator reaction. Taking sodium hydroxide as an example, the main reactions of the non-carbon components in the process are as follows:
NaOH+SiO2→Na2SiO3+H2O(5)
NaOH+Al2O3→NaAlO2+H2O(6)
NaOH+nSiO2·Al2O3→Na2SiO3+NaAlO2+H2O(7)
the main reactions of the carbon material in the activation process are as follows:
NaOH+-C-→Na+CO+H2O(8)
NaOH+-CH2-→Na2CO3+Na2O+H2(9)
NaOH+-COH→Na2CO3+H2(10)
NaOH+-COOH→Na2CO3+H2+H2O(11)
among them, the reactions (8) to (10) are easier to proceed because the initial reaction temperature is lower than that of the reaction (7).
Preferably, in the step (2), the second firing is performed in an inert atmosphere, a reducing atmosphere, or an atmosphere having an oxygen partial pressure of less than 1000 Pa.
In the preferable scheme, the primary roasting product and the secondary roasting product are washed until the pH value of washing liquor is 6-8.
In a preferable scheme, the washing liquid of the primary roasting product and the washing liquid of the secondary roasting product are mixed to be used as raw materials for recovering aluminum, sodium and sulfate.
The method carries out sulfating roasting treatment on the aluminum electrolysis anode carbon slag, volatilizes and recovers fluorine in a gaseous state, avoids the generation of high-temperature fluorine-containing flue gas and fluorine-containing wastewater, realizes the primary purification of the carbon slag, and utilizes the characteristic that concentrated sulfuric acid has strong oxidizing property, and is matched with an oxidant to introduce functional groups on the carbon material, thereby being beneficial to the subsequent activation and pore-forming. The alkali fusion process not only realizes the activation and pore-forming of the carbon material, but also further purifies the carbon material to obtain the high-purity porous material. The method does not generate high-temperature fluorine-containing flue gas and fluorine-containing wastewater in the treatment process, and can recover fluorine and aluminum elements to obtain the high-purity porous carbon material, thereby realizing the comprehensive recovery and cleaning treatment of the aluminum electrolysis anode carbon residue.
Compared with the prior art, the invention has the advantages that:
1. the invention utilizes the interaction of sulfuric acid and non-carbon components in the waste cathode carbon block to generate low-temperature fluorine-containing flue gas, and can solve the problem of equipment corrosion caused by high-temperature fluoride in the existing pyrogenic process; the highest treatment temperature in the process is not more than 300 ℃, so that the problems of high energy consumption and high equipment requirement of the conventional pyrogenic process can be avoided; in the process, fluorine is volatilized and recovered in a gaseous state, so that the problems of fluorine-containing wastewater, secondary pollution and the like in wet treatment can be solved.
2. The method can recover fluorine and aluminum elements in the waste cathode carbon block, obtain a high-purity porous carbon material, and realize efficient utilization of the waste cathode carbon block.
3. The invention skillfully utilizes the oxidation effect of the sulfating roasting process on the carbon material, so that the carbon material is promoted to activate and form pores, and the porous carbon material with large specific surface area is obtained.
Drawings
FIG. 1 is a process flow diagram of the method for recovering porous carbon from aluminum electrolysis anode carbon residue according to the present invention.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to examples and the accompanying drawings.
In the examples of the present invention, unless otherwise specified, the means employed are those conventional in the art, and the reagents employed are commercially available in a conventional manner.
Example 1
Uniformly mixing aluminum electrolysis anode carbon slag with the carbon content of 50% and the particle size of less than 0.50mm, 18.4mol/L sulfuric acid solution and sodium nitrate according to the mass ratio of 1:2:1 to obtain a mixture A, roasting the mixture A at 200 ℃ for 3 hours, namely, one-time roasting to obtain a one-time roasted product, wherein the fluorine removal rate is 99.1% in the process; washing and filtering the primary roasted product to be neutral, drying to obtain a product B, uniformly mixing the product B and sodium hydroxide according to the mass ratio of 1:5 to obtain a mixture C, roasting the mixture C at 1000 ℃ for 1 hour, and performing secondary roasting to obtain a secondary roasted product; washing and filtering the secondary roasting product to be neutral, and drying to obtain the product with the carbon content of 99.0 percent and the specific surface area of 2745m2A porous carbon material in g, as shown in Table 1.
Example 2
Uniformly mixing aluminum electrolysis anode carbon residue with the carbon content of 35% and the particle size of less than 0.40mm, 18mol/L sulfuric acid solution and sodium chlorate according to the mass ratio of 1:0.5:2 to obtain a mixture A, roasting the mixture A at 250 ℃ for 1 hour, namely, one-time roasting to obtain a one-time roasted product, wherein the fluorine removal rate is 98.0% in the process; washing and filtering the primary roasting product until the pH value is 6.5, drying to obtain a product B, uniformly mixing the product B and sodium carbonate according to the mass ratio of 1:7 to obtain a mixture C, and roasting the mixture C at 500 ℃ for 10 hours, namely secondary roasting to obtain a secondary roasting product; washing and filtering the secondary roasting product to be neutral, and drying to obtain the product with the carbon content of 99.3 percent and the specific surface area of 2158m2A porous carbon material in g, as shown in Table 1.
Example 3
Uniformly mixing aluminum electrolysis anode carbon slag with the carbon content of 90% and the particle size of less than 0.30mm and 17mol/L sulfuric acid solution according to the mass ratio of 1:5 to obtain a mixture A, roasting the mixture A at 150 ℃ for 5 hours, namely roasting once to obtain a roasted product, wherein the fluorine removal rate is 99.5% in the process; washing and filtering the primary roasting product to be neutral, drying to obtain a product B, uniformly mixing the product B with potassium hydroxide and potassium chloride according to the mass ratio of 1:1.5:1.5 to obtain a mixture C, roasting the mixture C at 700 ℃ for 5 hours, and performing secondary roasting to obtain a secondary roasting productBurning the product; washing and filtering the secondary roasting product to be neutral, and drying to obtain the product with the carbon content of 99.1 percent and the specific surface area of 2020m2A porous carbon material in g, as shown in Table 1.
Example 4
Uniformly mixing aluminum electrolysis anode carbon residue with the carbon content of 90% and the particle size of less than 0.30mm, 17mol/L sulfuric acid solution, nitric acid and sodium nitrate according to the mass ratio of 1:5:1:1 to obtain a mixture A, roasting the mixture A at 150 ℃ for 5 hours, wherein the roasting is carried out for one time to obtain a primary roasted product, and the fluorine removal rate is 99.4% in the process; washing and filtering the primary roasted product to be neutral, drying to obtain a product B, uniformly mixing the product B with potassium hydroxide and potassium chloride according to the mass ratio of 1:1.5:1.5 to obtain a mixture C, and roasting the mixture C at 700 ℃ for 5 hours, namely secondary roasting to obtain a secondary roasted product; washing and filtering the secondary roasting product to be neutral, and drying to obtain the product with the carbon content of 98.9 percent and the specific surface area of 2673m2A porous carbon material in g, as shown in Table 1.
Comparative example 1
Compared with the embodiment 1, the grain diameter of the aluminum electrolysis anode carbon residue is 1mm, other conditions are not changed, the fluorine removal rate after one-time roasting is 90.1 percent, the content of the obtained porous carbon is 94.3 percent, and the specific surface area is 1533m2In terms of/g, as shown in Table 1.
Comparative example 2
Compared with the example 1, the concentration of the used sulfuric acid is 10mol/L, other conditions are not changed, the fluorine removal rate after one-time roasting is 95.2 percent, the content of the obtained porous carbon is 97.4 percent, and the specific surface area is 2019m2In terms of/g, as shown in Table 1.
Comparative example 3
Compared with the embodiment 1, the mass ratio of the aluminum electrolysis anode carbon residue to the sulfuric acid to the sodium nitrate is 1:0.1:1, other conditions are not changed, the fluorine removal rate after one-time roasting is 30.2 percent, the content of the obtained porous carbon is 87.5 percent, and the specific surface area is 675m2In terms of/g, as shown in Table 1.
Comparative example 4
Compared with the embodiment 1, the mass ratio of the aluminum electrolysis anode carbon residue to the sulfuric acid to the sodium nitrate is 1:15:1, other conditions are not changed, and the fluorine removal rate after one-time roasting is realized99.2 percent, the content of the obtained porous carbon is 99.1 percent, and the specific surface area is 2853m2In terms of/g, as shown in Table 1.
Comparative example 5
Compared with the embodiment 1, the mass ratio of the aluminum electrolysis anode carbon residue to the sulfuric acid to the sodium nitrate is 1:2:7, other conditions are not changed, the fluorine removal rate after one-time roasting is 99.0 percent, the content of the obtained porous carbon is 89.9 percent, and the specific surface area is 2692m2In terms of/g, as shown in Table 1.
Comparative example 6
Compared with the example 1, the primary roasting temperature is 80 ℃, other conditions are unchanged, the fluorine removal rate after the primary roasting is 79.2 percent, the content of the obtained porous carbon is 91.3 percent, and the specific surface area is 1544m2In terms of/g, as shown in Table 1.
Comparative example 7
Compared with the example 1, the primary roasting temperature is 350 ℃, other conditions are unchanged, the fluorine removal rate after the primary roasting is 57.3 percent, the content of the obtained porous carbon is 81.4 percent, and the specific surface area is 1002m2In terms of/g, as shown in Table 1.
Comparative example 8
Compared with the example 1, the one-time roasting time is 0.1 hour, other conditions are not changed, the fluorine removal rate after the one-time roasting is 65.7 percent, the content of the obtained porous carbon is 82.3 percent, and the specific surface area is 976m2In terms of/g, as shown in Table 1.
Comparative example 9
Compared with the example 1, the one-time roasting time is 15 hours, other conditions are not changed, the fluorine removal rate after the one-time roasting is 99.3 percent, the content of the obtained porous carbon is 99.2 percent, and the specific surface area is 2815m2In terms of/g, as shown in Table 1.
Comparative example 10
Compared with the example 1, the product B is mixed with sodium hydroxide according to the mass ratio of 1:0.1, other conditions are not changed, the fluorine removal rate after primary roasting is 99.1 percent, the content of the obtained porous carbon is 97.5 percent, and the specific surface area is 1212m2In terms of/g, as shown in Table 1.
Comparative example 11
Compared with the example 1, the product B is mixed with sodium hydroxide according to the mass ratio of 1:15, and other conditions are not changed, namelyThe fluorine removal rate after the secondary roasting is 99.1 percent, the content of the obtained porous carbon is 99.3 percent, and the specific surface area is 2759m2In terms of/g, as shown in Table 1.
Comparative example 12
Compared with the example 1, the secondary roasting temperature is 200 ℃, other conditions are unchanged, the fluorine removal rate after the primary roasting is 99.1 percent, the content of the obtained porous carbon is 95.4 percent, and the specific surface area is 329m2In terms of/g, as shown in Table 1.
Comparative example 13
Compared with the example 1, the secondary roasting temperature is 1800 ℃, other conditions are unchanged, the fluorine removal rate after the primary roasting is 99.1 percent, the content of the obtained porous carbon is 98.7 percent, and the specific surface area is 689m2In terms of/g, as shown in Table 1.
Comparative example 14
Compared with the example 1, the secondary roasting time is 0.1 hour, other conditions are not changed, the fluorine removal rate after the primary roasting is 99.1 percent, the content of the obtained porous carbon is 97.6 percent, and the specific surface area is 795m2In terms of/g, as shown in Table 1.
Comparative example 15
Compared with the example 1, the secondary roasting time is 25 hours, other conditions are not changed, the fluorine removal rate after the primary roasting is 99.1 percent, the content of the obtained porous carbon is 99.4 percent, and the specific surface area is 1391m2In terms of/g, as shown in Table 1.
Comparative example 16
Compared with the embodiment 1, the first roasting is removed, the aluminum electrolysis anode carbon residue is directly mixed with sodium hydroxide for secondary roasting, other conditions are not changed, the content of the obtained porous carbon is 82.2 percent, and the specific surface area is 261m2In terms of/g, as shown in Table 1.
TABLE 1 physical Properties of porous carbons prepared in inventive examples 1-4 and comparative examples 1-16
As can be seen from the analysis in Table 1, the primary roasting step is beneficial to the fluorine removal, impurity removal and pore forming of the carbon slag; the addition of the oxidant in the primary roasting process is helpful for obtaining the porous carbon material with high specific surface area; too large carbon slag particle size, too dilute sulfuric acid concentration, too little acid addition, too low or too high primary roasting temperature and too short primary roasting time are not beneficial to fluorine removal, impurity removal and pore forming of the carbon slag; excessive acid, excessive oxidant, overlong primary roasting time and excessive activator addition do not contribute to fluorine removal, impurity removal and pore forming of the carbon slag, but waste resources; the excessively low secondary roasting temperature and the excessively short secondary roasting time are not beneficial to pore-forming and impurity removal of the carbon slag, but have no obvious influence on the removal of fluorine; the excessive secondary roasting temperature and the excessive secondary roasting time are not beneficial to the activation and pore-forming of the carbon slag, but have no obvious influence on the removal of fluorine and impurity removal.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (10)
1. A method for recovering porous carbon from aluminum electrolysis anode carbon slag is characterized by comprising the following steps:
(1) uniformly mixing aluminum electrolysis anode carbon residue, concentrated sulfuric acid and an oxidant according to the mass ratio of 1: 0.2-10: 0-5 to obtain a mixture A, and placing the mixture A at 100-300 ℃ for primary roasting to obtain a primary roasted product;
(2) washing, filtering and drying the primary roasting product to obtain a product B, uniformly mixing the product B and an activating agent according to the mass ratio of 1: 1-10 to obtain a mixture C, and roasting the mixture C at 300-1500 ℃ for the second time to obtain a secondary roasting product;
(3) and washing, filtering and drying the secondary roasting product to obtain the porous carbon material.
2. The method for recovering porous carbon from aluminum electrolysis anode carbon residue according to claim 1, wherein the concentration of the concentrated sulfuric acid is 15.0-18.4 mol/L.
3. The method for recovering porous carbon from aluminum electrolysis anode carbon residue according to claim 1, wherein the oxidant is at least one of cobalt trifluoride, sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, potassium dichromate, sodium dichromate, ammonium dichromate, potassium ferrate, potassium permanganate, sodium permanganate, ammonium permanganate, calcium permanganate, zinc permanganate, magnesium permanganate, potassium periodate, sodium periodate, potassium perchlorate, sodium perchlorate, potassium chlorate, sodium chlorate, magnesium chlorate, potassium nitrate, sodium nitrate, ammonium nitrate, and nitric acid.
4. The method for recovering porous carbon from aluminum electrolysis anode carbon residue according to claim 1, wherein in the step (1), the mixture A is subjected to primary roasting at 150-250 ℃.
5. The method for recovering porous carbon from aluminum electrolysis anode carbon residue according to claim 1, wherein in the step (1), the primary roasting time is 0.1-10 hours.
6. The method for recovering porous carbon from aluminum electrolysis anode carbon residue according to claim 1, wherein in the step (1), the flue gas generated by primary roasting is absorbed and recovered with an alumina dry method.
7. The method for recovering porous carbon from aluminum electrolysis anode carbon residue according to claim 1, wherein the activating agent is at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium chloride and potassium chloride.
8. The method for recovering porous carbon from aluminum electrolysis anode carbon residue according to claim 1, wherein in the step (2), the mixture C is subjected to secondary roasting at 500-1000 ℃.
9. The method for recovering porous carbon from aluminum electrolysis anode carbon residue according to claim 1, wherein in the step (2), the secondary roasting time is 0.1-20 hours.
10. The method for recovering porous carbon from aluminum electrolysis anode carbon residue according to claim 1, wherein in the step (2), the secondary calcination is performed in an inert atmosphere, a reducing atmosphere or an atmosphere with an oxygen partial pressure of less than 1000 Pa.
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