CN111017972B - Resource separation and recycling method of aluminum ash - Google Patents
Resource separation and recycling method of aluminum ash Download PDFInfo
- Publication number
- CN111017972B CN111017972B CN201911298271.9A CN201911298271A CN111017972B CN 111017972 B CN111017972 B CN 111017972B CN 201911298271 A CN201911298271 A CN 201911298271A CN 111017972 B CN111017972 B CN 111017972B
- Authority
- CN
- China
- Prior art keywords
- aluminum
- aluminum ash
- filter residue
- naoh
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/10—Compounds containing silicon, fluorine, and other elements
- C01B33/103—Fluosilicic acid; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/02—Halides of titanium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A resource separation and recycling method of aluminum ash comprises the following steps: (1) preparing aluminum ash after washing; preparing a sodium hydroxide solution; (2) placing the sodium hydroxide solution into a reactor, stirring and gradually adding the washed aluminum ash, and discharging generated hydrogen and ammonia; (3) when the discharge of hydrogen and ammonia is stopped, adding water for dilution and stirring, and filtering to obtain primary filtrate; (4) adding hydrofluoric acid into the primary filtrate under the stirring condition until the pH value is 3-5 to obtain a solid-liquid mixture; (5) filtering to obtain secondary filtrate and secondary filter residue; drying the secondary filter residue to obtain cryolite; concentrating the secondary filtrate to prepare Na 2 SiF 6 The product of (1). The method of the invention leads the aluminum ash to be separated, recycled and utilized as resources.
Description
Technical Field
The invention relates to the technical field of recovery and treatment of dangerous waste solid materials generated in aluminum smelting, in particular to a resource separation and recovery utilization method of aluminum ash.
Background
Aluminum is the most resourceful metal on earth, second only to steel in production. Aluminum has light weight and good oxidation and corrosion resistance, can form aluminum alloy with a plurality of metal elements and has different purposes and recyclability. The aluminum is produced by a method of electrolyzing aluminum oxide by cryolite flux molten salt; at present, the design production capacity of the electrolytic cell in China reaches more than 4000 ten thousand tons per year, the actual aluminum yield is about 3700 ten thousand tons per year, and the actual aluminum yield exceeds 4000 ten thousand tons per year in addition to the large amount of waste aluminum recovery and secondary smelting.
Aluminum applications are applied in various aspects, essentially in the form of various aluminum alloy materials. Part of the aluminum material is added with intermediate alloy of various alloy elements from original aluminum melt in an electrolytic aluminum plant, and then is subjected to degassing and deslagging to be cast into an aluminum alloy material. The other part is subjected to slag removal by an electrolytic aluminum plant, cast into a common aluminum ingot, then transported to an aluminum product manufacturer, melted, added with intermediate alloy of alloy elements, and then subjected to degassing and impurity removal to prepare an aluminum alloy material; therefore, the actual amount of aluminum and aluminum alloy to be cast may exceed 5000 ten thousand tons per year. Aluminum ash is generated in the process of casting various aluminum and aluminum alloys, and the amount of the generated aluminum ash is different according to different aluminum alloy casting products, such as cast aluminum alloy (aluminum silicon), and the generated aluminum ash is about 70 kg/t; the aviation aluminum material is about 35 kg/t; the raw aluminum casting (common aluminum ingot) is about 5 kg/t; and the other aluminum alloys are about 20 kg/t; on average, the aluminum ash is about 20kg/t, and the amount of the aluminum ash is about 100 million tons/year according to 5000 million tons/year of aluminum and aluminum alloy materials.
The aluminum ash has complex chemical components, the main components are aluminum oxide, aluminum nitride and fine metallic aluminum, other components have great difference according to different alloy components and different purifying agent raw materials and covering agent raw materials, and the typical aluminum ash components are given by the following data:
TABLE 1 chemical composition (% by mass) of several typical aluminum ashes
It can be seen from the data analysis in the table that the main components in the aluminum ash include silicon oxide, iron oxide and oxides and fluorides of magnesium and calcium, but these analysis data are not completely accurate, because the data in the table do not give analysis data of metal aluminum and aluminum nitride in the aluminum ash, actually, the maximum component content of the aluminum ash except for aluminum oxide should be metal aluminum and aluminum nitride, wherein the content of aluminum is about 10-20%, and the difference is different according to the difference of one aluminum ash treatment method, the component of aluminum nitride in the aluminum ash should be about 15%, and the typical elemental analysis data of the aluminum ash given by the same data are calculated as follows:
TABLE 2 typical elemental analysis (% by mass) of aluminum ash
| Al | Cl | F | Na | Mg | Si | K | Ca | Fe | O | C | N | Others |
| 40.46 | 7.70 | 2.69 | 8.63 | 0.78 | 1.40 | 1.29 | 0.64 | 0.25 | 26.01 | 0.08 | 4.78 | 5.30 |
The aluminum ash is a byproduct in smelting and refining aluminum and aluminum alloy, and soluble chloride and fluoride of alkali metal potassium and sodium are contained in the aluminum ash, and NH is generated by hydrolysis of the nitride in water 3 And water-soluble NaAlO produced by the reaction 2 (ii) a It has an impact on the environment and is considered to be a toxic and harmful solid waste.
At present, many researches on methods for treating and recycling aluminum ash are carried out, and the methods are mostly found in published and issued patents, and the methods are difficult to be reviewed in a listing manner, but can be summarized into the following categories:
one type of method is the preparation of aluminum hydroxide or alumina from aluminum ash, as disclosed in patents CN108239704A, CN105271327A, CN104261445A, CN106830023A, CN108439444A, CN108529658A, CN1224723C, CN106830030A, CN109928413A, CN1903725A, etc.; although the patents have slight differences, the principle and the method are basically the same, namely, the aluminum ash is washed by water, soluble substances (mainly chloride) in the aluminum ash are removed, then the aluminum ash is mixed with sodium carbonate, sodium hydroxide or lime (CaO), sintering is carried out at the temperature of more than 700-900 ℃, the alumina in the aluminum ash is converted into water-soluble aluminate, the generated sodium aluminate is leached by water, and then the aluminum hydroxide and the alumina are prepared by the carbon separation and seed separation process of the sodium aluminate.
In addition to the preparation of alumina or aluminum hydroxide from aluminum ash by the above method, CN1817795A reacts the sodium aluminate prepared by the above method with sulfuric acid to produce aluminum hydroxide precipitate and sodium sulfate solution, which is then subjected to solid-liquid separation to prepare aluminum hydroxide; CN101144020A is to react the aluminum ash with sulfuric acid to prepare aluminum sulfate, and to react with sodium aluminate prepared by the reaction of the aluminum ash and alkali to prepare aluminum hydroxide; in CN107758682A, sodium aluminate prepared from aluminum ash is reacted with sodium phosphate to prepare zeolite. From the above, it can be seen that there are many patented methods for preparing alumina from aluminum ash; however, so far, there is noIn any of the methods, the following problems are encountered: (1) the aluminum ash has complex components, and although various alloys produce different aluminum ashes, a common characteristic of the aluminum ash is that each aluminum ash contains impurity iron (Fe) 2 O 3 ) But also contains high levels of silicon impurities, oxides and fluorides of magnesium and calcium. As for the silicon impurity, it exists in the form of silica in the aluminum ash, and such silicon impurity is inevitably present in the products of the above-mentioned various patented processes without being removed and treated; (2) the product is single, and the other products except the aluminum hydroxide can not be recycled.
Patent CN101823741B discloses another treatment method of aluminum ash, which comprises the steps of firstly roasting the aluminum ash after water immersion at the temperature of 750-900 ℃, then soaking the aluminum ash in dilute hydrofluoric acid containing sodium nitrate or ozone, filtering, concentrating and evaporating the filtrate to obtain a solid product, producing aluminum fluoride by using the existing industrial cryolite production method, reacting the evaporated solution with sodium hydroxide, producing water glass according to the existing water glass production technology, and obtaining high-fluorine alumina containing magnesium fluoride as filter residue; the method has the problems that the process is complicated, and calcium oxide and iron oxide with high impurity content in aluminum ash cannot be effectively removed, so that the prepared fluorine-containing aluminum oxide has low purity and is difficult to be applied in practice.
In addition to the above methods, CN100532268C authorizes a method of extracting alumina by acid dissolution using hydrochloric acid, and CN108585003A extracts alumina by leaching with sulfuric acid. These methods do not address the problem of purification of silica, calcium fluoride, calcium oxide, magnesium fluoride and iron impurities in the aluminum ash, which are high in other components. In practice, the acid treatment of the recovered aluminum ash to obtain alumina of higher purity may be a more complicated process and may result in a large amount of acid-containing waste residues. In addition to the use of acid treatment of aluminum ash to produce water purification agents, the use of acid treatment of aluminum ash to produce alumina has not been commercially viable.
Disclosure of Invention
Aiming at the research current situation and the existing problems of the recycling treatment and the resource utilization of the aluminum ash, the invention provides a resource separation recycling method of the aluminum ash.
The method of the invention is carried out according to the following steps:
1. preparing aluminum ash after washing; preparing a sodium hydroxide solution with the mass concentration of 15-35%; the amount of the sodium hydroxide solution is calculated according to Al, AlN and SiO in the aluminum ash obtained after NaOH and water are washed 2 Completely reacting, and adding 10-50% of excessive amount; the complete reaction is based on the formula:
Al+NaOH+H 2 O＝NaAlO 2 +1.5H 2 (1)、
AlN+NaOH+H 2 O＝NH 3 +NaAlO 2 (2)
and
SiO 2 +2NaOH＝Na 2 SiO 3 +H 2 O (3)；
2. putting a sodium hydroxide solution into a reactor, adding the washed aluminum ash into the reactor in batches and in a successive manner under the condition of stirring, reacting Al and AlN in the washed aluminum ash with NaOH to generate hydrogen and ammonia gas, and discharging and collecting the hydrogen and ammonia gas from an exhaust pipe of the reactor;
3. after all the washed aluminum ash is added into the reactor, stopping discharging hydrogen and ammonia gas in the reactor, and finishing the reaction; adding water to the reacted solid-liquid mixed material for dilution and stirring for 5-20 minutes, wherein the adding amount of the water is 1-5 times of the total volume of the solid-liquid mixed material, and then filtering to obtain primary filter residue and primary filtrate;
4. adding hydrofluoric acid with the mass concentration of 40-60% into the primary filtrate under the stirring condition until the pH value of the primary filtrate is 3-5 to ensure that NaAlO in the primary filtrate 2 Reacting with NaOH and HF to generate cryolite precipitate, and adding Na in the primary filtrate 2 SiO 3 Reaction with HF to form Na 2 SiF 6 Obtaining cryolite-containing precipitate and Na-containing precipitate 2 SiF 6 A solid-liquid mixture of the solution;
5. filtering the solid-liquid mixture to obtain secondary filtrate and secondary filter residue; drying the secondary filter residue to remove water to obtain a cryolite product; evaporating and concentrating the secondary filtrate to obtain Na as main component 2 SiF 6 The product of (1).
The main chemical component of the primary filter residue is alpha-Al 2 O 3 、β-Al 2 O 3 CaO and MgO, and also contains a small amount of Fe 2 O 3 And directly discharging.
In the above primary filter residue, when Fe 2 O 3 When the mass percentage of the aluminum oxide is less than or equal to 0.3 percent, drying the primary filter residue to be used as an aluminum oxide raw material when the aluminum electrolytic cell is roasted and started.
In the above primary filter residue, when Fe 2 O 3 In percentage by mass of>0.3%, Fe in the primary filter residue was analyzed 2 O 3 CaO and MgO contents; pickling the primary filter residue in hydrochloric acid to obtain Fe 2 O 3 Reacting CaO and MgO with hydrochloric acid, dissolving, and filtering to obtain acid-washed filter residue; the dosage of the hydrochloric acid is determined by HCl and Fe in the primary filter residue 2 O 3 And CaO and MgO are subjected to complete reaction, and the complete reaction is based on the following reaction formula:
Fe 2 O 3 +6HCl＝2FeCl 3 +3H 2 O (4)、
MgO+2HCl＝MgCl 2 +H 2 o (5) and
CaO+2HCl＝CaCl 2 +H 2 O (6)；
and then drying the acid-washing filter residue to be used as an alumina raw material when the aluminum electrolytic cell is started to roast.
In the step 1, the amount of the sodium hydroxide solution is determined according to Al, AlN and SiO in the aluminum ash obtained by washing NaOH and water 2 Completely reacting, and controlling the NaAlO generated by the reaction while the excessive amount is 10-50 percent 2 And residual NaOH, so that NaAlO is used in step 4 2 When NaOH and HF react to generate cryolite precipitate, NaF and AlF in the generated cryolite precipitate 3 Mole ofThe ratio is n, wherein n is more than or equal to 1 and less than or equal to 3.
In the step 2, when the washed aluminum ash is added to the reactor in batches, the bubble foam generated by the reaction is controlled not to overflow the reactor.
The mass concentration of the hydrochloric acid is 10-25%.
The washed aluminum ash contains TiO 2 In this case, Na is also contained in the primary filtrate 2 TiO 3 (ii) a After hydrofluoric acid is added in step 4, Na 2 TiO 3 Reacting with hydrofluoric acid to form water-soluble Na 2 TiF 6 (ii) a After evaporation concentration in step 5, Na is prepared as the main component 2 SiF 6 And Na 2 TiF 6 The product of (1).
In the invention, after sodium hydroxide solution and water are used for washing to remove soluble chloride, sodium fluoride and potassium fluoride, aluminum nitride, aluminum and silicon oxide in the residual material react, and the generated ammonia gas and hydrogen gas are recovered; generated NaAlO 2 Neutralizing the rest NaOH with HF to prepare cryolite; the main component is alpha-Al 2 O 3 And beta-Al 2 O 3 The primary filter residue can be used as an alumina raw material when the aluminum electrolytic cell is roasted and started after iron is removed, so that the aluminum ash is separated, recycled and utilized as resources.
Detailed Description
The invention uses aluminum ash as aluminum ash slag generated in the aluminum alloy casting production process of an electrolytic aluminum plant, and after most of metal aluminum is extracted by using the conventional aluminum extraction method, the generated aluminum ash containing 5-20% of metal aluminum in percentage by mass is also called secondary aluminum ash in the industry.
The washed aluminum ash is prepared by washing secondary aluminum ash with water to remove water-soluble components and then drying or semi-drying.
The sodium hydroxide used in the examples of the present invention was commercially available sodium hydroxide of commercial purity.
The hydrofluoric acid used in the examples of the present invention was commercial industrial grade hydrofluoric acid.
The hydrochloric acid used in the examples of the present invention was commercial industrial grade hydrochloric acid.
In the embodiment of the invention, the dried filter residue is used as the high-calcium high-magnesium aluminum oxide raw material when the aluminum electrolytic cell is started to roast.
Example 1
Preparing aluminum ash (chemical components are Al according to mass percent) after washing 2 O 3 54.2％，SiO 2 1.5％，Al 13.5％，AlN 16％，Fe 2 O 3 0.3％，Ca(Mg)O+Ca(Mg)F 2 11%, others 3.5%); preparing a sodium hydroxide solution with the mass concentration of 15-35%; the amount of the sodium hydroxide solution is calculated according to Al, AlN and SiO in the aluminum ash obtained after NaOH and water are washed 2 Completely reacting, and carrying out 10-50% excess;
putting a sodium hydroxide solution into a reactor, adding the washed aluminum ash into the reactor in batches and in a successive manner under the condition of stirring, reacting Al and AlN in the washed aluminum ash with NaOH to generate hydrogen and ammonia gas, and discharging and collecting the hydrogen and ammonia gas from an exhaust pipe of the reactor; when the washed aluminum ash is added into the reactor in batches and successively, controlling the bubble foam generated by the reaction not to overflow the reactor;
after all the washed aluminum ash is added into the reactor, stopping discharging hydrogen and ammonia gas in the reactor, and finishing the reaction; adding water to the reacted solid-liquid mixed material for dilution and stirring for 5-20 minutes, wherein the adding amount of the water is 1-5 times of the total volume of the solid-liquid mixed material, and then filtering to obtain primary filter residue and primary filtrate;
adding hydrofluoric acid with the mass concentration of 40-60% into the primary filtrate under the stirring condition until the pH value of the primary filtrate is 3-5 to ensure that NaAlO in the primary filtrate 2 Reacting with NaOH and HF to generate cryolite precipitate, and adding Na in the primary filtrate 2 SiO 3 Reaction with HF to form Na 2 SiF 6 Obtaining cryolite-containing precipitate and Na-containing precipitate 2 SiF 6 A solid-liquid mixture of the solution;
wherein the excess of sodium hydroxide solution is determined by NaAlO 2 When NaOH and HF react to generate cryolite precipitate, NaF and AlF in the generated cryolite precipitate 3 The molar ratio of n is n, wherein n is more than or equal to 1 and less than or equal to 3;
filtering the solid-liquid mixture to obtain secondary filtrate and secondary filter residue;drying the secondary filter residue to remove water to obtain a cryolite product; evaporating and concentrating the secondary filtrate to obtain Na as main component 2 SiF 6 The product of (1);
the main chemical component of the primary filter residue is alpha-Al 2 O 3 、β-Al 2 O 3 CaO and MgO, and also contains a small amount of Fe 2 O 3 And directly discharging.
Example 2
The method is the same as example 1, except that:
fe in primary filter residue 2 O 3 The mass percentage content of the aluminum oxide is less than or equal to 0.3 percent, and the aluminum oxide is used as an aluminum oxide raw material when the aluminum electrolytic cell is roasted and started after being dried.
Example 3
The method is the same as example 1, except that:
fe in primary filter residue 2 O 3 In percentage by mass of>0.3%, Fe in the first residue was analyzed 2 O 3 CaO and MgO contents; pickling the primary filter residue in hydrochloric acid with the mass concentration of 10-25% to enable Fe in the primary filter residue 2 O 3 Reacting CaO and MgO with hydrochloric acid, dissolving, and filtering to obtain acid-washed filter residue; the dosage of the hydrochloric acid is determined by HCl and Fe in the primary filter residue 2 O 3 CaO and MgO complete reaction; and then drying the acid-washing filter residue to be used as an alumina raw material when the aluminum electrolytic cell is started to roast.
Claims (6)
1. A resource separation and recycling method of aluminum ash is characterized by comprising the following steps:
(1) preparing aluminum ash after washing; preparing a sodium hydroxide solution with the mass concentration of 15-35%; the amount of the sodium hydroxide solution is calculated according to Al, AlN and SiO in the aluminum ash obtained after NaOH and water are washed 2 Completely reacting, and carrying out 10-50% excess; the complete reaction is based on the formula:
Al + NaOH + H 2 O = NaAlO 2 + 1.5H 2 （1）、
AlN+ NaOH + H 2 O = NH 3 + NaAlO 2 （2）
and
SiO 2 + 2NaOH = Na 2 SiO 3 + H 2 O （3）；
(2) putting a sodium hydroxide solution into a reactor, adding the washed aluminum ash into the reactor in batches and in a successive manner under the condition of stirring, reacting Al and AlN in the washed aluminum ash with NaOH to generate hydrogen and ammonia gas, and discharging and collecting the hydrogen and ammonia gas from an exhaust pipe of the reactor;
(3) after all the washed aluminum ash is added into the reactor, stopping discharging hydrogen and ammonia gas in the reactor, and finishing the reaction; adding water to the reacted solid-liquid mixed material for dilution and stirring for 5-20 minutes, wherein the adding amount of the water is 1-5 times of the total volume of the solid-liquid mixed material, and then filtering to obtain primary filter residue and primary filtrate;
(4) adding hydrofluoric acid with the mass concentration of 40-60% into the primary filtrate under the stirring condition until the pH value of the primary filtrate is 3-5 to ensure that NaAlO in the primary filtrate 2 Reacting with NaOH and HF to generate cryolite precipitate, and adding Na in the primary filtrate 2 SiO 3 Reaction with HF to form Na 2 SiF 6 Obtaining cryolite-containing precipitate and Na-containing precipitate 2 SiF 6 A solid-liquid mixture of the solution;
(5) filtering the solid-liquid mixture to obtain secondary filtrate and secondary filter residue; drying the secondary filter residue to remove water to obtain a cryolite product; evaporating and concentrating the secondary filtrate to obtain the product with Na as main component 2 SiF 6 The product of (1);
wherein in the step (1), the amount of the sodium hydroxide solution is calculated according to Al, AlN and SiO in the aluminum ash obtained by washing NaOH and water 2 Completely reacting, and controlling the NaAlO generated by the reaction while the excessive amount is 10-50 percent 2 And residual NaOH, so that NaAlO is used in step (4) 2 When NaOH and HF react to generate cryolite precipitate, NaF and AlF in the generated cryolite precipitate 3 The molar ratio of n is n, wherein n is more than or equal to 1 and less than or equal to 3.
2. The method for resource recovery and separation of aluminum ash as claimed in claim 1, wherein the main chemical components of the first residue areIs alpha-Al 2 O 3 、β-Al 2 O 3 CaO and MgO, and also contains a small amount of Fe 2 O 3 And directly discharging.
3. The method for resource recovery and separation of aluminum ash as claimed in claim 1, wherein Fe is contained in the first residue 2 O 3 When the mass percentage of the aluminum oxide is less than or equal to 0.3 percent, drying the primary filter residue to be used as an aluminum oxide raw material when the aluminum electrolytic cell is roasted and started.
4. The method for resource recovery and separation of aluminum ash as claimed in claim 1, wherein Fe is contained in the first residue 2 O 3 In percentage by mass of>At 0.3%, Fe in the primary residue was analyzed 2 O 3 CaO and MgO contents; pickling the primary filter residue in hydrochloric acid to obtain Fe 2 O 3 Reacting CaO and MgO with hydrochloric acid, dissolving, and filtering to obtain acid-washed filter residue; the dosage of the hydrochloric acid is determined by HCl and Fe in the primary filter residue 2 O 3 And CaO and MgO are subjected to complete reaction, and the complete reaction is based on the following reaction formula:
Fe 2 O 3 + 6HCl=2FeCl 3 + 3H 2 O （4）、
MgO + 2HCl= MgCl 2 + H 2 o (5) and
CaO + 2HCl= CaCl 2 + H 2 O （6）；
and then drying the acid-washing filter residue to be used as an alumina raw material when the aluminum electrolytic cell is started to roast.
5. The method according to claim 1, wherein in the step (2), when the washed aluminum ash is added to the reactor in a batch-wise manner, the bubble bubbles generated by the reaction are controlled not to overflow the reactor.
6. The resource separation and recovery utilization method of aluminum ash as claimed in claim 4, wherein the mass concentration of hydrochloric acid is 10-25%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911298271.9A CN111017972B (en) | 2019-12-17 | 2019-12-17 | Resource separation and recycling method of aluminum ash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911298271.9A CN111017972B (en) | 2019-12-17 | 2019-12-17 | Resource separation and recycling method of aluminum ash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111017972A CN111017972A (en) | 2020-04-17 |
| CN111017972B true CN111017972B (en) | 2022-08-05 |
Family
ID=70209195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911298271.9A Active CN111017972B (en) | 2019-12-17 | 2019-12-17 | Resource separation and recycling method of aluminum ash |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111017972B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111547754B (en) * | 2020-05-19 | 2022-09-27 | 河南联宜环保科技有限公司 | Method for converting regenerated cryolite into aluminum fluoride |
| CN111807829A (en) * | 2020-07-15 | 2020-10-23 | 沈阳北冶冶金科技有限公司 | Method for preparing magnesia-alumina spinel by using aluminum ash and bischofite |
| CN113003594A (en) * | 2021-02-06 | 2021-06-22 | 达州励志环保科技有限公司 | Method for producing cryolite |
| CN113072089B (en) * | 2021-03-26 | 2022-08-05 | 广西博世科环保科技股份有限公司 | Method for recovering cryolite by combined treatment of aluminum electrolysis overhaul slag and aluminum ash |
| CN114182103A (en) * | 2021-11-26 | 2022-03-15 | 天津天一爱拓科技有限公司 | Method for resource utilization of aluminum ash and household garbage incineration fly ash through cooperative treatment |
| CN114632509B (en) * | 2022-03-25 | 2023-04-21 | 昆明理工大学 | Preparation of Cr-Al by using aluminium-chromium slag 2 O 3 Method for preparing mesoporous catalytic material and application thereof |
| CN115215292A (en) * | 2022-06-29 | 2022-10-21 | 广东至道先进土木工程材料技术研究有限公司 | Method for preparing hydrogen by using secondary aluminum ash |
| CN115611657B (en) * | 2022-09-26 | 2023-12-19 | 科达制造股份有限公司 | Lightweight aggregate with aluminum ash as raw material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4362703A (en) * | 1982-03-01 | 1982-12-07 | Iowa State University Research Foundation, Inc. | Process for preparing cryolite from fly ash |
| CN101323461A (en) * | 2008-07-24 | 2008-12-17 | 河南未来铝业（集团）有限公司 | Method for synthesizing cryolite by using waste from aluminum fluoride and trihydrate alumina production |
| CN101823741A (en) * | 2010-02-03 | 2010-09-08 | 中南大学 | Method for continuously producing aluminium electrolysis raw materials high-fluorine alumina, cryolite and sodium silicate with aluminum dust |
| CN108059178A (en) * | 2017-12-29 | 2018-05-22 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | A kind of method that Aluminum subtracts the waste liquid production ice crystal of slag |
| CN108103526A (en) * | 2017-11-13 | 2018-06-01 | 昆明理工大学 | A kind of method using electrolytic aluminium aluminium ash purifying electrolysis aluminium flue gas and recycling bauxite resource |
| CN108147444A (en) * | 2017-12-29 | 2018-06-12 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | A kind of system and technique of Alkaline etchant production ice crystal |
| CN108220603A (en) * | 2017-11-09 | 2018-06-29 | 昆明冶金研究院 | A kind of aluminium ash recovery process of normal pressure alkali leaching-sulfuric acid curing-hot acid-leaching |
-
2019
- 2019-12-17 CN CN201911298271.9A patent/CN111017972B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4362703A (en) * | 1982-03-01 | 1982-12-07 | Iowa State University Research Foundation, Inc. | Process for preparing cryolite from fly ash |
| CN101323461A (en) * | 2008-07-24 | 2008-12-17 | 河南未来铝业（集团）有限公司 | Method for synthesizing cryolite by using waste from aluminum fluoride and trihydrate alumina production |
| CN101823741A (en) * | 2010-02-03 | 2010-09-08 | 中南大学 | Method for continuously producing aluminium electrolysis raw materials high-fluorine alumina, cryolite and sodium silicate with aluminum dust |
| CN108220603A (en) * | 2017-11-09 | 2018-06-29 | 昆明冶金研究院 | A kind of aluminium ash recovery process of normal pressure alkali leaching-sulfuric acid curing-hot acid-leaching |
| CN108103526A (en) * | 2017-11-13 | 2018-06-01 | 昆明理工大学 | A kind of method using electrolytic aluminium aluminium ash purifying electrolysis aluminium flue gas and recycling bauxite resource |
| CN108059178A (en) * | 2017-12-29 | 2018-05-22 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | A kind of method that Aluminum subtracts the waste liquid production ice crystal of slag |
| CN108147444A (en) * | 2017-12-29 | 2018-06-12 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | A kind of system and technique of Alkaline etchant production ice crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111017972A (en) | 2020-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111017972B (en) | Resource separation and recycling method of aluminum ash | |
| US7670407B2 (en) | Method of producing titanium | |
| CN111233003B (en) | Acid-base combined process for completely realizing resource utilization of high-fluorine secondary aluminum ash | |
| US7906097B2 (en) | Processes for treating aluminium dross residues | |
| KR101502592B1 (en) | slag treatment method for extracting silic and magnesia | |
| CN113278808B (en) | Method for recovering various solid waste materials in aluminum smelting process in linkage manner | |
| US2823991A (en) | Process for the manufacture of titanium metal | |
| CN112340759A (en) | Method for preparing polyaluminum chloride and recovering silicon simple substance by using secondary aluminum ash | |
| CN112695205A (en) | Method for environment-friendly resource utilization of copper smelting slag | |
| CN109811371B (en) | Method for preparing aluminum-silicon alloy from low-grade aluminum resources | |
| US5939035A (en) | Process for treating spent potlining containing inorganic matter | |
| CN108118143A (en) | Two sections of chloridising roastings-alkaline leaching method puies forward the method that lithium prepares lithium carbonate from lepidolite | |
| CN111807829A (en) | Method for preparing magnesia-alumina spinel by using aluminum ash and bischofite | |
| JP3796929B2 (en) | Almidros residual ash treatment method | |
| CN112981122B (en) | Method for recovering sodium and vanadium in sodium-modified vanadium extraction tailings | |
| US2547901A (en) | Process for the manufacture of alkali metal aluminum fluoride | |
| CN111270092B (en) | Method for decomposing mixed rare earth ore | |
| CN115216630B (en) | Recycling treatment method of waste lithium-containing aluminum electrolyte | |
| JPH11319753A (en) | Treatment of aluminum dross residual ash | |
| CN115537564A (en) | Comprehensive recovery method for electrolytic slag | |
| CN112390264B (en) | Method for improving desilication rate of coal gangue by aluminum ash catalysis | |
| Mwepu et al. | Lithium extraction from Zimbabwean petalite using ammonium bifluoride | |
| CN115572083A (en) | Aluminum ash resource utilization process and cement clinker | |
| WO2023044537A1 (en) | A process for producing alumina | |
| CN113061755A (en) | Process for producing ammonium paratungstate by flotation type tungsten raw material oxygen-enriched leaching full-wet method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |