CN113636602A - Method for preparing molten iron by reducing fluorine content in waste sulfuric acid by using aluminum sludge - Google Patents
Method for preparing molten iron by reducing fluorine content in waste sulfuric acid by using aluminum sludge Download PDFInfo
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- CN113636602A CN113636602A CN202110790663.8A CN202110790663A CN113636602A CN 113636602 A CN113636602 A CN 113636602A CN 202110790663 A CN202110790663 A CN 202110790663A CN 113636602 A CN113636602 A CN 113636602A
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- CN
- China
- Prior art keywords
- fluorine
- sulfuric acid
- ions
- waste
- aluminum
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- 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.)
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- 239000002699 waste material Substances 0.000 abstract 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 6
- 239000011737 fluorine Substances 0.000 abstract 6
- 229910052731 fluorine Inorganic materials 0.000 abstract 6
- 239000002253 acid Substances 0.000 abstract 4
- 229910052782 aluminium Inorganic materials 0.000 abstract 4
- -1 fluorine ions Chemical class 0.000 abstract 4
- 238000000034 method Methods 0.000 abstract 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 3
- 239000007788 liquid Substances 0.000 abstract 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 239000010802 sludge Substances 0.000 abstract 2
- 235000011121 sodium hydroxide Nutrition 0.000 abstract 2
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract 2
- 238000003756 stirring Methods 0.000 abstract 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910001430 chromium ion Inorganic materials 0.000 abstract 1
- 229910001610 cryolite Inorganic materials 0.000 abstract 1
- 235000003891 ferrous sulphate Nutrition 0.000 abstract 1
- 239000011790 ferrous sulphate Substances 0.000 abstract 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 229910000358 iron sulfate Inorganic materials 0.000 abstract 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 229910001453 nickel ion Inorganic materials 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 229910001415 sodium ion Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a method for preparing molten iron by reducing the fluorine content in waste sulfuric acid by using aluminum sludge, which comprises the following steps: adding aluminum mud into the fluorine-containing waste sulfuric acid, stirring for dissolving, and uniformly mixing; adding iron powder into the step (1) to react with acid and ferric iron in the system; adding liquid caustic soda into the step (2), adjusting the pH value and introducing sodium ions to enable fluorine ions and chromium ions to form precipitates; and (4) adding sodium sulfide into the step (3), uniformly stirring, removing nickel ions in the solution, and carrying out solid-liquid separation to obtain a ferrous sulfate solution. Aiming at the problems that the fluorine-containing waste sulfuric acid is difficult to treat, a large amount of sludge is generated in the treatment process, and the treatment cost is high, the invention provides the method for utilizing aluminum ions in aluminum mud to react with fluorine ions in the waste acid to finally produce cryolite precipitate so as to reduce the content of the fluorine ions in the waste acid, and utilizing liquid caustic soda and sodium sulfide to remove heavy metals in the waste acid to obtain the molten iron sulfate as a water treatment agent; the waste is treated by waste, the waste is changed into valuable, and the method has good economic and social benefits.
Description
Technical Field
The invention relates to the field of waste resource recycling in aluminum alloy casting and steel pickling industries, in particular to a method for preparing molten iron by reducing the content of fluorine in waste sulfuric acid by using aluminum sludge.
Background
The aluminum mud is waste corrosion liquid, waste washing liquid, waste tank liquid, tank slag and wastewater treatment sludge generated by metal or plastic surface acid (alkali) washing, oil removal, rust removal, washing, phosphorization, brightening and chemical polishing processes. Because the aluminum mud contains toxic and harmful substances to the environment, the aluminum mud is listed as surface treatment waste (HW17) in the national hazardous waste records, and the hazardous property is toxicity (T/C). The components of the aluminum mud have certain differences due to different generation raw materials and production processes.
The waste acid is corrosive solution containing iron ions and other heavy metals generated in the steel pickling surface treatment process. Since the waste acid contains toxic and harmful substances to the environment, the waste acid is listed as non-ferrous metal smelting waste (HW34) in the national hazardous waste list, and the hazardous property is toxicity (C, T). The waste acid components have certain difference due to different generation raw materials and production processes, and part of the waste acid components need to be added with hydrofluoric acid, so that a large amount of fluorine ions are contained in the waste acid, and the treatment cost is obviously increased.
The invention discloses a method for removing fluorinion in water body, which comprises air-drying aluminum sludge, and grinding to particle size of 1-5 mm; cleaning the aluminum sludge with pure water, soaking the aluminum sludge in dilute sulfuric acid, filtering, adding the filtered filter residue into an activating agent for activation, filtering again, placing the filtered filter residue into a muffle furnace, and preserving heat for 0.5-1h at the temperature of 500-550 ℃ to obtain activated aluminum sludge. However, the patent process is complex, high-temperature roasting is needed, and the investment and operation cost is high.
The invention discloses a high-efficiency low-cost fluoride ion adsorbent and a preparation method and application thereof in Chinese patent CN 103962089A. Soluble iron salt, aluminum salt, manganese salt and sodium hydroxide are used as raw materials, a composite oxide precipitate of an iron, aluminum and manganese three-system is synthesized by a solution precipitation reaction method, and then the high-efficiency and low-cost adsorbent is obtained by washing, dehydrating and drying. Mixing the obtained adsorbent with coal powder and starch according to a certain proportion, balling in a balling mill, and drying to obtain the efficient and cheap fluorine ion adsorbent. However, the patent process is complex, high-temperature roasting is needed, and the investment and operation cost is high.
The invention discloses a method for preparing cryolite by using fluorine-containing waste acid, which comprises the steps of adding a vulcanizing agent into waste water, precipitating to remove heavy metal ions and impurities in the waste water, filtering, and reserving filtrate; adding sodium salt and aluminum salt into the filtrate, stirring for reaction, and filtering to obtain a filter cake; and washing the filter cake with water and drying to obtain the cryolite. However, the patent has the problems of product purification, complex process, large energy consumption and the like.
The invention discloses a method for removing fluorinion in wastewater, which comprises the steps of sequentially adding a calcium hydroxide solution, an aluminum sulfate solution and a polymeric flocculant, and carrying out solid-liquid separation after precipitation. However, the process is complex, different pH values need to be controlled, and the equipment investment is large.
The invention provides a method for removing fluorine and chloride ions from high-concentration industrial waste acid, which is characterized in that rare earth hydroxide solution and a fluorine removing agent of oxalic acid are added into the high-concentration industrial waste acid for defluorination treatment to obtain a slag phase and a liquid phase; then, carrying out alkali dissolution separation on the defluorinated slag phase to obtain soluble fluoride and rare earth hydroxide precipitate. However, the method has the disadvantages of complex raw materials, complex process and high cost.
The prior art method for treating fluoride ions in waste liquid mainly has the following defects:
1. the preparation process of the fluoride ion adsorbent is complex, a large amount of energy is consumed for activation and drying, and the investment and operation cost is high;
2. the method for directly removing the fluoride ions in the waste liquid has complex process, needs various different reagents and has higher operation cost.
Disclosure of Invention
The invention aims to provide a method for preparing molten iron by reducing the content of fluorine in waste sulfuric acid by using aluminum sludge, aiming at solving the problems that the existing fluorine-containing waste sulfuric acid is difficult to treat, a large amount of sludge is generated in the treatment process, and the treatment cost is high.
Aiming at the defects of the prior art, the invention provides a method for preparing ferrous sulfate solution by reacting hazardous waste aluminum mud with fluorine-containing waste sulfuric acid at normal temperature, adding iron powder to consume acid and reduce ferric iron, adjusting pH by using liquid alkali to precipitate chromium ions and fluorine ions in the solution, adding sodium sulfide to precipitate nickel ions, and performing solid-liquid separation.
The invention relates to a method for removing fluorine by using the reaction of aluminum mud and fluorine-containing waste sulfuric acid, which comprises the following steps:
(1) adding aluminum mud into the fluorine-containing waste sulfuric acid, stirring for dissolving, and uniformly mixing;
(2) adding iron powder into the step (1) to react with acid and ferric iron in the system;
(3) adding liquid caustic soda into the step (2), adjusting the pH value and introducing sodium ions to enable fluorine ions and chromium ions to form precipitates;
(4) and (4) adding sodium sulfide into the step (3), uniformly stirring, removing nickel ions in the solution, and carrying out solid-liquid separation to obtain a ferrous sulfate solution.
Preferably, the mass of the aluminum mud added in the step (1) is 1-1.4 times equivalent of the content of fluorine ions in the fluorine-containing waste sulfuric acid, and the stirring time is 0.5-1 h;
preferably, the amount of the iron powder added in the step (2) is 1.1 to 1.3 times equivalent of the content of the acid and the ferric iron in the solution, and the stirring time is 1 to 3 hours;
preferably, the concentration of the added liquid caustic soda in the step (3) is 15% -30%, the pH is adjusted to 4.2-4.5, and the stirring time is 0.5-1 h;
preferably, the amount of the sodium sulfide added in the step (4) is 5-10 times of the equivalent of the nickel ion content in the solution, and the stirring time is 0.5-1 h.
Aiming at the problems that the fluorine-containing waste sulfuric acid is difficult to treat, a large amount of sludge is generated in the treatment process, and the treatment cost is high, the invention provides the method for utilizing aluminum ions in aluminum mud to react with fluorine ions in the waste acid to finally produce cryolite precipitate so as to reduce the content of the fluorine ions in the waste acid, and utilizing liquid caustic soda and sodium sulfide to remove heavy metals in the waste acid to obtain ferrous sulfate water as a water treatment agent or further prepare products such as polymeric ferric sulfate and the like. The waste is treated by waste, the waste is changed into valuable, and the method has good economic and social benefits.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, but the technical solutions do not limit the scope of the present invention.
Example 1
Crushing aluminum mud, adding the crushed aluminum mud into fluorine-containing waste sulfuric acid (the fluorine content is 12355ppm), stirring for 30min, adding a proper amount of iron powder, stirring until the content of ferric iron in the solution is less than 0.1%, supplementing a proper amount of water, adding liquid alkali to adjust the pH to 4.32, adding a proper amount of sodium sulfide to remove heavy metals, continuously stirring for 30min, and carrying out solid-liquid separation to obtain a ferrous sulfate solution, wherein the iron content is 5.66%, and the fluorine ion content is 229.95 ppm.
Example 2
Crushing aluminum mud, adding the crushed aluminum mud into fluorine-containing waste sulfuric acid (the fluorine content is 12355ppm), stirring for 30min, adding a proper amount of iron powder, stirring until ferric iron in the solution is reduced into ferrous iron, supplementing a proper amount of water, adding liquid alkali to adjust the pH to 4.43, adding a proper amount of sodium sulfide to remove heavy metals, continuously stirring for 60min, and carrying out solid-liquid separation to obtain a ferrous sulfate solution, wherein the iron content is 5.02% and the fluorine ion content is 148.79 ppm.
Example 3
Crushing aluminum mud, adding the crushed aluminum mud into waste sulfuric acid containing fluorine (the fluorine content is 12700ppm), stirring for 30min, adding a proper amount of iron powder, stirring until ferric iron in the solution is reduced into ferrous iron, supplementing a proper amount of water, adding liquid alkali to adjust the pH to 4.46, adding a proper amount of sodium sulfide to remove heavy metals, continuously stirring for 30min, and carrying out solid-liquid separation to obtain a ferrous sulfate solution, wherein the iron content is 4.44%, and the fluorine ion content is 161.17 ppm.
Example 4
Crushing aluminum mud, adding the crushed aluminum mud into waste sulfuric acid containing fluorine (the fluorine content is 13562ppm), stirring for 40min, adding a proper amount of iron powder, stirring until the ferric iron content in the solution is less than 0.1%, supplementing a proper amount of water, adding liquid alkali to adjust the pH to 4.35, adding a proper amount of sodium sulfide to remove heavy metals, continuously stirring for 30min, and carrying out solid-liquid separation to obtain a ferrous sulfate solution, wherein the iron content is 5.17%, and the fluorine ion content is 180.04 ppm.
Example 5
Crushing aluminum mud, adding the crushed aluminum mud into waste sulfuric acid containing fluorine (the fluorine content is 13562ppm), stirring for 40min, adding a proper amount of iron powder, stirring until the ferric iron content in the solution is less than 0.1%, supplementing a proper amount of water, adding liquid alkali to adjust the pH to 4.43, adding a proper amount of sodium sulfide to remove heavy metals, continuously stirring for 30min, and carrying out solid-liquid separation to obtain a ferrous sulfate solution, wherein the iron content is 5.02%, and the fluorine ion content is 148.79 ppm.
Example 6
Crushing aluminum mud, adding the crushed aluminum mud into waste sulfuric acid containing fluorine (the fluorine content is 13562ppm), stirring for 40min, adding a proper amount of iron powder, stirring until the ferric iron content in the solution is less than 0.1%, supplementing a proper amount of water, adding liquid alkali to adjust the pH to 4.51, adding a proper amount of sodium sulfide to remove heavy metals, continuously stirring for 30min, and carrying out solid-liquid separation to obtain a ferrous sulfate solution, wherein the iron content is 4.95%, and the fluorine ion content is 135.15 ppm.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (6)
1. A method for preparing molten iron by reducing the fluorine content in waste sulfuric acid by using aluminum sludge is characterized by comprising the following steps:
(1) adding aluminum mud into the fluorine-containing waste sulfuric acid, stirring for dissolving, and uniformly mixing;
(2) adding iron powder into the step (1) to react with acid and ferric iron in the system;
(3) adding liquid caustic soda into the step (2), adjusting the pH value and introducing sodium ions to enable fluorine ions and chromium ions to form precipitates;
(4) and (4) adding sodium sulfide into the step (3), uniformly stirring, removing nickel ions in the solution, and carrying out solid-liquid separation to obtain a ferrous sulfate solution.
2. The method for preparing the molten iron by using the aluminum sludge to reduce the fluorine content in the waste sulfuric acid, according to claim 1, wherein the method comprises the following steps: the mass of the aluminum mud added in the step (1) is 1-1.4 times of the equivalent weight of the fluorine ion content in the fluorine-containing waste sulfuric acid, and the stirring time is 0.5-1 h.
3. The method for preparing the molten iron by using the aluminum sludge to reduce the fluorine content in the waste sulfuric acid, as claimed in claim 2, wherein: the mass of the aluminum mud added in the step (1) is 1.2 times of equivalent of the content of fluorine ions in the fluorine-containing waste sulfuric acid, and the stirring time is 0.5 h.
4. The method for preparing the molten iron by using the aluminum sludge to reduce the fluorine content in the waste sulfuric acid, according to claim 1, wherein the method comprises the following steps: the amount of the iron powder added in the step (2) is 1.1 to 1.3 times of the equivalent of the content of the acid and the ferric iron in the solution, and the stirring time is 1 to 3 hours.
5. The method for preparing the molten iron by using the aluminum sludge to reduce the fluorine content in the waste sulfuric acid, according to claim 1, wherein the method comprises the following steps: and (3) adding liquid caustic soda with the concentration of 15% -30%, adjusting the pH value to 4.2-4.5, and stirring for 0.5-1 h.
6. The method for preparing molten iron by using aluminum sludge to reduce the fluorine content in waste sulfuric acid according to claim 5, wherein: and (4) adding sodium sulfide in an amount which is 5-10 times of the equivalent of the nickel ion content in the solution, and stirring for 0.5-1 h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110790663.8A CN113636602A (en) | 2021-07-13 | 2021-07-13 | Method for preparing molten iron by reducing fluorine content in waste sulfuric acid by using aluminum sludge |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110790663.8A CN113636602A (en) | 2021-07-13 | 2021-07-13 | Method for preparing molten iron by reducing fluorine content in waste sulfuric acid by using aluminum sludge |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105480997A (en) * | 2016-01-20 | 2016-04-13 | 武汉工程大学 | Method for preparing cryolite from fluorine-containing waste acid produced during smelting |
| CN107758716A (en) * | 2017-12-11 | 2018-03-06 | 达州励志环保科技有限公司 | A kind of utilize smelts the method that fluorine-containing spent acid prepares ice crystal |
| CN111018192A (en) * | 2019-12-30 | 2020-04-17 | 斯瑞尔环境科技股份有限公司 | Method for preparing high-purity ferrous iron by using heavy metal ions in ferrous solution precipitated by sodium sulfide solid |
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2021
- 2021-07-13 CN CN202110790663.8A patent/CN113636602A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105480997A (en) * | 2016-01-20 | 2016-04-13 | 武汉工程大学 | Method for preparing cryolite from fluorine-containing waste acid produced during smelting |
| CN107758716A (en) * | 2017-12-11 | 2018-03-06 | 达州励志环保科技有限公司 | A kind of utilize smelts the method that fluorine-containing spent acid prepares ice crystal |
| CN111018192A (en) * | 2019-12-30 | 2020-04-17 | 斯瑞尔环境科技股份有限公司 | Method for preparing high-purity ferrous iron by using heavy metal ions in ferrous solution precipitated by sodium sulfide solid |
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Application publication date: 20211112 |