CN110980833A - Preparation method of electronic-grade ferrous chloride - Google Patents
Preparation method of electronic-grade ferrous chloride Download PDFInfo
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Abstract
The invention discloses a preparation method of electronic grade ferrous chloride. The method for producing the electronic grade ferrous chloride has the advantages of simple production principle, wide raw material source, low cost and easy industrial production. The method comprises the steps of pumping the iron-containing waste hydrochloric acid which is subjected to pretreatment and reduction impurity removal into a three-effect evaporation system for evaporation concentration, cooling, centrifuging and filtering to obtain ferrous chloride tetrahydrate crystals, and if the crystals do not reach the control index of the electronic-grade ferrous chloride, performing repeated recrystallization until the electronic-grade ferrous chloride reaching the control standard is obtained, wherein the centrifuged mother liquor can be directly used for producing the water treatment agent ferric chloride, and no secondary pollutant is generated in the whole process. Meanwhile, the defects that ferrous ions are easily oxidized into ferric iron at a higher temperature and ferric iron is easily hydrolyzed when the acidity is insufficient, the product turns yellow, and the storage is difficult in the traditional production process are avoided. The invention is used in the technical field of energy material preparation.
Description
Technical Field
The invention relates to the technical field of resource utilization of iron-containing waste hydrochloric acid, in particular to a preparation method of an electronic-grade ferrous chloride product.
Background
The clean energy sources researched by human beings include solar energy, hydrogen energy, wind energy, biological energy, geothermal energy, tidal energy and the like, but most of the clean energy sources have the characteristic of discontinuity in time and space, so that an efficient energy storage device is very important for the development of the clean energy sources.
The lithium battery is also called as a lithium ion secondary battery, has the advantages of high energy density, cleanness, no pollution, long cycle life and the like, is widely applied to modern energy storage equipment, is also considered as a power supply with the most development and application prospect, such as a mobile phone, a notebook computer, a camera and the like, which all need the lithium ion battery with high energy density, and the lithium ion battery is used in the aspect of modern life, greatly enriches the requirements of modern life and brings convenience to the life of human beings.
The traditional lithium ion battery adopts LiCoO2As a positive electrode material, the material cannot meet the requirements of practical application due to the problems of high cost, resource shortage, environmental pollution and the like. Polyanionic Li2FeSiO4The material is a new positive electrode material, is favored because of high Si storage capacity and superior performances of low cost, environmental protection, no pollution, high theoretical capacity and the like of the battery, and the important iron source material for preparing the lithium iron silicate is high-purity ferrous chloride.
The traditional preparation process of ferrous chloride generally comprises the steps of adding excessive iron powder into hydrochloric acid with a certain concentration, then carrying out filter pressing, carrying out reduced pressure concentration on obtained filtrate at 70-110 ℃ to a certain specific gravity, cooling, stirring and crystallizing to obtain ferrous chloride crystals, and carrying out centrifugal separation by a centrifugal machine to obtain ferrous chloride solids. Iron powder and hydrochloric acid are subjected to violent chemical reaction to release heat and hydrogen, the control conditions are inappropriate, explosion is easy to occur, and casualties are caused.
Disclosure of Invention
The invention aims to solve the technical problems, and provides a preparation method of electronic-grade ferrous chloride, which comprises the steps of pumping iron-containing waste hydrochloric acid which is subjected to pretreatment and reduction impurity removal into a three-effect evaporation system for evaporation concentration, cooling, centrifuging and filtering to obtain ferrous chloride tetrahydrate crystals, dissolving the crystals with dilute acid water if the crystals do not reach the control index of the electronic-grade ferrous chloride, then performing operations such as evaporation concentration, cooling, centrifuging and filtering to obtain secondary crystals, if the secondary crystals are still unqualified, performing the same recrystallization method until the electronic-grade ferrous chloride meeting the control standard is obtained, and directly using the centrifuged mother liquor for producing the water treatment agent.
In order to solve the technical problems, the invention adopts the technical scheme that:
1. a preparation method of electronic grade ferrous chloride comprises the following steps:
(1) after the waste hydrochloric acid containing iron is thrown into a stirring tank, a certain amount of reducing agent is added, so that a small amount of ferric iron in the waste hydrochloric acid containing iron is reduced into ferrous iron;
(2) carrying out filter pressing on the iron-containing waste hydrochloric acid subjected to reduction and impurity removal in the step (1) by a filter press or filtering the iron-containing waste hydrochloric acid by a pipeline filter;
(3) feeding the feed liquid reduced in the step (2) as a raw material for producing electronic-grade ferrous chloride into a triple-effect evaporation system for concentration;
(4) when the material-liquid ratio or the solid-liquid ratio in the step (3) meets the control requirement, discharging the material to the crystallization kettle, and introducing cooling water to a jacket of the crystallization kettle;
(5) when the temperature of the material liquid in the kettle reaches the control requirement, separating the material liquid by a centrifugal machine to obtain primary crystallization of ferrous chloride tetrahydrate, and inspecting;
(6) if the primary crystallization in the step (5) reaches the control index of the electronic-grade ferrous chloride, filling nitrogen for split charging and storage, otherwise, dissolving the primary crystallization, sending the dissolved primary crystallization into a triple-effect evaporator for evaporation and concentration until the specific gravity or solid-liquid ratio of the feed liquid reaches the control requirement, then discharging the material into a crystallization kettle, cooling the material in the kettle by introducing cooling water into a jacket of the crystallization kettle, separating the material by a centrifugal machine when the temperature of the material in the kettle reaches the control requirement, obtaining secondary crystallization of the ferrous chloride tetrahydrate, and sending for inspection;
(7) if the secondary crystallization in the step (6) reaches the control index of the electronic-grade ferrous chloride, filling nitrogen for split charging and storage, otherwise, dissolving the primary crystallization with dilute acid water, sending the dissolved crystal into a triple-effect evaporator for evaporation and concentration until the specific gravity of the feed liquid or the solid-liquid ratio reaches the control requirement, then discharging the crystal kettle, introducing cooling water into a jacket of the crystal kettle to cool the material in the kettle, and when the temperature of the material in the kettle reaches the control requirement, separating the material by a centrifugal machine to obtain the ferrous chloride tetrahydrate for triple crystallization and sending the crystal for inspection;
(8) and by analogy, obtaining the qualified electronic grade ferrous chloride product through repeated recrystallization.
By adopting the technical scheme, the hydrochloric acid and the ferric salt in the iron-containing waste hydrochloric acid are separated through triple-effect evaporation concentration mainly according to the characteristics that hydrogen chloride is easy to volatilize and is soluble in water and the solubility rule of ferrous chloride in an acid solution, HCl-containing gas generated by evaporation is condensed and separated to obtain 0.5-10% of dilute hydrochloric acid, and the condensate can be secondarily utilized to dissolve unqualified ferrous chloride crystals, so that the waste of water resources and the increase of the wastewater treatment capacity are avoided. In addition, the heavy metals such as Mn, Zn and the like in the iron-containing waste hydrochloric acid can be effectively removed in a mode of repeated recrystallization and centrifugal filtration, the process is simple, the operation risk coefficient is low, and the qualified high-yield high-added-value electronic grade ferrous chloride product is obtained.
Preferably, the iron-containing waste hydrochloric acid in the step (1) is obtained from the metallurgy and metal processing industry, in order to improve the surface property of steel, hydrochloric acid is adopted to process the surface of the steel so as to remove oxidized rusty objects on the surface of the steel, when the acid content is reduced to a certain degree, the pickling speed is reduced, the acid needs to be discharged to replace new acid, and the discharged waste liquid is the iron-containing waste hydrochloric acid.
Preferably, the reducing agent in the step (1) is scrap iron, iron sheet, iron net, ring iron or sodium bisulfite.
Preferably, the iron-containing waste hydrochloric acid in the step (2) is filtered by a pipeline filter with a filter bag of 100-300 microns or is subjected to pressure filtration by a filter press with filter cloth of 800-1300 meshes.
Preferably, the specific gravity of the feed liquid discharged into the crystallization kettle in the step (4) is 1.40-1.50, or the solid-liquid ratio is 5% -35%, and more preferably, the specific gravity of the feed liquid is controlled to be 1.45, or the solid-liquid volume ratio is controlled to be 20%.
Preferably, the temperature of the feed liquid discharged to the centrifuge in the step (5) is 20-40 ℃.
Preferably, the control indexes of the electronic grade ferrous chloride are as follows: FeCl2·4H2O，≥98％；Fe3+，≤0.15％；Mn，≤0.018％；Cr，≤0.0012％；Zn，≤0.0011％。
Preferably, the solvent for dissolving the unqualified ferrous chloride tetrahydrate crystals in the step (6) is evaporated dilute acid water.
Preferably, the acidity (as HCl) of the dilute acid water is 0.5 to 10%.
Preferably, the step (8) is followed by directly using the centrifuged mother liquor for producing the water treatment agent ferric trichloride.
In summary, the technical scheme of the invention has the following beneficial effects:
1. the production method of the electronic grade ferrous chloride has the advantages of simple principle, easily obtained raw materials, low cost and easy mass production.
2. The implementation of the technical scheme of the invention promotes the resource utilization of the waste hydrochloric acid containing iron, changes waste into valuable, and is more beneficial to the protection of ecological environment and the harmonious development of nature and human.
3. According to the invention, hydrochloric acid and ferric salt in the iron-containing waste hydrochloric acid are separated by triple-effect evaporation concentration mainly according to the characteristics that hydrogen chloride is easy to volatilize and easy to dissolve in water and the solubility rule of ferrous chloride in an acidic solution, HCl-containing gas generated by evaporation is condensed and separated to obtain 0.5-10% of dilute hydrochloric acid, and the condensate can be secondarily utilized to dissolve unqualified ferrous chloride crystals, so that the waste of water resources and the increase of the wastewater treatment amount are avoided. In addition, heavy metals such as Mn, Zn and the like in the iron-containing waste hydrochloric acid can be effectively removed in a mode of repeated recrystallization and centrifugal filtration, the process is simple, the operation risk coefficient is low, the centrifuged mother liquor is directly used for producing the water treatment agent ferric trichloride, and secondary pollutants are not generated in the whole process.
4. The technical scheme of the invention can realize the industrial production of the electronic grade ferrous chloride.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, but the technical solutions do not limit the scope of the present invention.
Referring to fig. 1, the preparation method of electronic grade ferrous chloride provided by the invention comprises the following steps:
(1) after the waste hydrochloric acid containing iron is thrown into a stirring tank, a certain amount of reducing agent is added, so that a small amount of ferric iron in the waste hydrochloric acid containing iron is reduced into ferrous iron;
(2) carrying out filter pressing on the iron-containing waste hydrochloric acid subjected to reduction and impurity removal in the step (1) by a filter press or filtering the iron-containing waste hydrochloric acid by a pipeline filter;
(3) feeding the feed liquid reduced in the step (2) as a raw material for producing electronic-grade ferrous chloride into a triple-effect evaporation system for concentration;
(4) when the material-liquid ratio or the solid-liquid ratio in the step (3) meets the control requirement, discharging the material to the crystallization kettle, and introducing cooling water to a jacket of the crystallization kettle;
(5) when the temperature of the material liquid in the kettle reaches the control requirement, separating the material liquid by a centrifugal machine to obtain primary crystallization of ferrous chloride tetrahydrate, and inspecting;
(6) if the primary crystallization in the step (5) reaches the control index of the electronic-grade ferrous chloride, filling nitrogen for split charging and storage, otherwise, dissolving the primary crystallization, sending the dissolved primary crystallization into a triple-effect evaporator for evaporation and concentration until the specific gravity or solid-liquid ratio of the feed liquid reaches the control requirement, then discharging the material into a crystallization kettle, cooling the material in the kettle by introducing cooling water into a jacket of the crystallization kettle, separating the material by a centrifugal machine when the temperature of the material in the kettle reaches the control requirement, obtaining secondary crystallization of the ferrous chloride tetrahydrate, and sending for inspection;
(7) if the secondary crystallization in the step (6) reaches the control index of the electronic-grade ferrous chloride, filling nitrogen for split charging and storage, otherwise, dissolving the primary crystallization with dilute acid water, sending the dissolved crystal into a triple-effect evaporator for evaporation and concentration until the specific gravity of the feed liquid or the solid-liquid ratio reaches the control requirement, then discharging the crystal kettle, introducing cooling water into a jacket of the crystal kettle to cool the material in the kettle, and when the temperature of the material in the kettle reaches the control requirement, separating the material by a centrifugal machine to obtain the ferrous chloride tetrahydrate for triple crystallization and sending the crystal for inspection;
(8) and by analogy, obtaining the qualified electronic grade ferrous chloride product through repeated recrystallization.
The following description will be given with reference to specific examples:
example 1
(1) And (3) pumping the iron-containing waste hydrochloric acid into a stirring tank, adding excessive scrap iron, stirring for 30min, and feeding the mixture to the triple effect evaporation after passing through a filter with the pore diameter of 300 mu m.
(2) When the specific gravity of the evaporated feed liquid reaches 1.45, the material is discharged to the crystallization kettle, and cooling water is introduced into the jacket of the crystallization kettle.
(3) When the temperature of the feed liquid in the crystallization kettle is reduced to 35 ℃, discharging the feed liquid to a centrifugal machine to obtain primary crystallization of ferrous chloride tetrahydrate, and detecting the FeCl of the primary crystallization2·4H2O content 96.8%, Fe3+The content of Mn was 0.014%, the content of Cr was 0.0008%, and the content of Zn was 0.0009%.
(4) And (4) dissolving the primary crystallization in the step (3) by using dilute acid with the acid content of 1.2 percent, and directly pumping the obtained solution into an evaporation system for concentration.
(5) When the specific gravity of the evaporated feed liquid reaches 1.43, the material is discharged to the crystallization kettle, and cooling water is introduced into the jacket of the crystallization kettle.
(6) When the temperature of the feed liquid in the crystallization kettle is reduced to 33 ℃, discharging the feed liquid to the crystallization kettle to obtain secondary crystallization of ferrous chloride tetrahydrate, and detecting the FeCl of the secondary crystallization2·4H2O content of 97.8%, Fe3+The content of Mn was 0.16%, the content of Mn was 0.008%, the content of Cr was 0.0006%, and the content of Zn was 0.0005%.
(7) And (4) dissolving the secondary crystallization in the step (6) by using dilute acid with the acid content of 3.1 percent, and directly pumping the obtained solution into an evaporation system for concentration.
(8) When the specific gravity of the feed liquid reaches 1.46, the feed liquid starts to be discharged to the crystallization kettle, and cooling water is introduced into a jacket of the crystallization kettle.
(9) When the temperature of the feed liquid in the crystallization kettle is reduced to 32 ℃, discharging the feed liquid to the crystallization kettle to obtain three-time crystallization of ferrous chloride tetrahydrate, and detecting FeCl of the three-time crystallization2·4H2O content 98.8%, Fe3+The content of the Mn-Zn alloy is 0.13 percent, the content of the Mn is 0.007 percent, the content of the Cr is 0.0004 percent, the content of the Zn is 0.0004 percent, and the control standard of electronic-grade ferrous chloride products is achieved.
Example 2
(1) And (3) pumping the iron-containing waste hydrochloric acid into a stirring tank, adding excessive scrap iron, stirring for 30min, and feeding the mixture to the triple effect evaporation after passing through a 200-micron pore size filter.
(2) When the specific gravity of the evaporated feed liquid reaches 1.40, the material is discharged to the crystallization kettle, and cooling water is introduced into the jacket of the crystallization kettle.
(3) When the temperature of the feed liquid in the crystallization kettle is reduced to 37 ℃, discharging the feed liquid to a centrifugal machine to obtain primary crystallization of ferrous chloride tetrahydrate, and detecting the FeCl of the primary crystallization2·4H2O content 97.1%, Fe3+The content of Mn is 0.16%, the content of Mn is 0.019%, the content of Cr is 0.0014%, and the content of Zn is 0.001%.
(4) Dissolving the primary crystallization in the step (3) with dilute acid with the acid content of 2.1 percent, and directly pumping the obtained solution into an evaporation system for concentration.
(5) When the specific gravity of the evaporated feed liquid reaches 1.44, the material is discharged to the crystallization kettle, and cooling water is introduced into the jacket of the crystallization kettle.
(6) When the temperature of the feed liquid in the crystallization kettle is reduced to 32 ℃, discharging the feed liquid to the crystallization kettle to obtain secondary crystallization of ferrous chloride tetrahydrate, and detecting the FeCl of the secondary crystallization2·4H2O content of 99.1%, Fe3+The content of the iron-based alloy is 0.08 percent, the content of Mn is 0.011 percent, the content of Cr is 0.009 percent, the content of Zn is 0.0004 percent, and the iron-based alloy reaches the control standard of electronic-grade ferrous chloride products.
Example 3
(1) And pumping the iron-containing waste hydrochloric acid into a stirring tank, adding excessive scrap iron, stirring for 30min, performing filter pressing by a filter press with 1300-mesh filter cloth, and feeding by triple effect evaporation.
(2) When the specific gravity of the evaporated feed liquid reaches 1.50, the material is discharged to the crystallization kettle, and cooling water is introduced into the jacket of the crystallization kettle.
(3) When the temperature of the feed liquid in the crystallization kettle is reduced to 25 ℃, discharging the feed liquid to a centrifugal machine to obtain primary crystallization of ferrous chloride tetrahydrate, and detecting the FeCl of the primary crystallization2·4H2O content 97.4%, Fe3+The content of Mn is 0.16%, the content of Mn is 0.02%, the content of Cr is 0.0012%, and the content of Zn is 0.0015%.
(4) And (4) dissolving the primary crystallization in the step (3) by using dilute acid with the acid content of 1.8 percent, and directly pumping the obtained solution into an evaporation system for concentration.
(5) When the specific gravity of the evaporated feed liquid reaches 1.42, the material is discharged to the crystallization kettle, and cooling water is introduced into the jacket of the crystallization kettle.
(6) When the temperature of the feed liquid in the crystallization kettle is reduced to 21 ℃, discharging the feed liquid to the crystallization kettle to obtain secondary crystallization of ferrous chloride tetrahydrate, and detecting the FeCl of the secondary crystallization2·4H2O content 98.9%, Fe3+The content is 0.011 percent, the content of Mn is 0.008 percent, the content of Cr is 0.0008 percent, the content of Zn is 0.001 percent, and the control standard of electronic-grade ferrous chloride products is reached.
Example 4
(1) And (3) beating the iron-containing waste hydrochloric acid into a stirring tank, adding excessive scrap iron, stirring for 30min, performing filter pressing by a filter press with 800-mesh filter cloth, and feeding by triple effect evaporation.
(2) When the specific gravity of the evaporated feed liquid reaches 1.47, the material is discharged to the crystallization kettle, and cooling water is introduced into the jacket of the crystallization kettle.
(3) When the temperature of the feed liquid in the crystallization kettle is reduced to 33 ℃, discharging the feed liquid to a centrifugal machine to obtain primary crystallization of ferrous chloride tetrahydrate, and detecting the FeCl of the primary crystallization2·4H2O content of 99.2%, Fe3+The content of the iron-based alloy is 0.13 percent, the content of Mn is 0.013 percent, the content of Cr is 0.0009 percent, and the content of Zn is 0.0007 percent, so as to reach the control standard of electronic-grade ferrous chloride products.
According to the embodiments, the production of the electronic grade ferrous chloride product can be realized through 1-3 times of recrystallization, the operation is simple, the raw material source is wide, the cost is low, and the purity of the prepared ferrous chloride product is high.
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 (10)
1. The preparation method of the electronic grade ferrous chloride is characterized by comprising the following steps:
(1) after the waste hydrochloric acid containing iron is thrown into a stirring tank, a certain amount of reducing agent is added, so that a small amount of ferric iron in the waste hydrochloric acid containing iron is reduced into ferrous iron;
(2) carrying out filter pressing on the iron-containing waste hydrochloric acid subjected to reduction and impurity removal in the step (1) by a filter press or filtering the iron-containing waste hydrochloric acid by a pipeline filter;
(3) feeding the feed liquid reduced in the step (2) as a raw material for producing electronic-grade ferrous chloride into a triple-effect evaporation system for concentration;
(4) when the material-liquid ratio or the solid-liquid ratio in the step (3) meets the control requirement, discharging the material to the crystallization kettle, and introducing cooling water to a jacket of the crystallization kettle;
(5) when the temperature of the material liquid in the kettle reaches the control requirement, separating the material liquid by a centrifugal machine to obtain primary crystallization of ferrous chloride tetrahydrate, and inspecting;
(6) if the primary crystallization in the step (5) reaches the control index of the electronic-grade ferrous chloride, filling nitrogen for split charging and storage, otherwise, dissolving the primary crystallization, sending the dissolved primary crystallization into a triple-effect evaporator for evaporation and concentration until the specific gravity or solid-liquid ratio of the feed liquid reaches the control requirement, then discharging the material into a crystallization kettle, cooling the material in the kettle by introducing cooling water into a jacket of the crystallization kettle, separating the material by a centrifugal machine when the temperature of the material in the kettle reaches the control requirement, obtaining secondary crystallization of the ferrous chloride tetrahydrate, and sending for inspection;
(7) if the secondary crystallization in the step (6) reaches the control index of the electronic-grade ferrous chloride, filling nitrogen for split charging and storage, otherwise, dissolving the primary crystallization with dilute acid water, sending the dissolved crystal into a triple-effect evaporator for evaporation and concentration until the specific gravity of the feed liquid or the solid-liquid ratio reaches the control requirement, then discharging the crystal kettle, introducing cooling water into a jacket of the crystal kettle to cool the material in the kettle, and when the temperature of the material in the kettle reaches the control requirement, separating the material by a centrifugal machine to obtain the ferrous chloride tetrahydrate for triple crystallization and sending the crystal for inspection;
(8) and by analogy, obtaining the qualified electronic grade ferrous chloride product through repeated recrystallization.
2. The method for preparing electronic grade ferrous chloride according to claim 1, wherein the iron-containing waste hydrochloric acid in step (1) is obtained from metallurgy and metal processing industry, in order to improve the surface property of steel, the surface of the steel is processed by hydrochloric acid to remove oxidized rust on the surface of the steel, when the acid content is reduced to a certain degree, the pickling speed is reduced, new acid needs to be discharged to replace, and the discharged waste liquid is the iron-containing waste hydrochloric acid.
3. The method for preparing electronic grade ferrous chloride according to claim 1, wherein the reducing agent in step (1) is scrap iron, iron sheet, iron mesh, iron coil or sodium bisulfite.
4. The preparation method of electronic grade ferrous chloride according to claim 1, wherein the iron-containing waste hydrochloric acid in the step (2) is filtered by a pipeline filter with 100-300 μm filter bags or is filter-pressed by a filter press with 800-1300 mesh filter cloth.
5. The preparation method of electronic grade ferrous chloride according to claim 1, wherein the specific gravity of the feed liquid in the step (4) when the feed liquid is discharged into the crystallization kettle is 1.40-1.50, or the solid-liquid ratio is 5-35%.
6. The preparation method of electronic grade ferrous chloride according to claim 1, wherein the temperature of the feed liquid when the feed liquid is discharged into the centrifuge in the step (5) is 20-40 ℃.
7. The method for preparing electronic grade ferrous chloride according to claim 1, wherein the control indexes of the electronic grade ferrous chloride are as follows: FeCl2·4H2O，≥98％；Fe3+，≤0.15％；Mn，≤0.018％；Cr，≤0.0012％；Zn，≤0.0011％。
8. The method for preparing electronic grade ferrous chloride according to claim 1, wherein the solvent for dissolving the unqualified ferrous chloride tetrahydrate crystal in step (6) is dilute acid water which is evaporated.
9. The method for preparing electronic grade ferrous chloride according to claim 1, wherein the acidity (as HCl) of the dilute acid water is 0.5-10%.
10. The method for preparing electronic grade ferrous chloride according to claim 1, wherein the step (8) is followed by directly using the centrifuged mother liquor for producing water treatment agent ferric trichloride.
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Cited By (5)
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| CN113213548A (en) * | 2021-05-13 | 2021-08-06 | 斯瑞尔环境科技股份有限公司 | Packaging method of ferrous chloride crystal |
| CN114014372A (en) * | 2021-11-26 | 2022-02-08 | 吉林省益能科技有限公司 | Preparation process of ferric trichloride solution |
| US20220204358A1 (en) * | 2020-12-29 | 2022-06-30 | 3r Environmental Technology Co., Ltd. | Method for purifying ferric chloride |
| CN115947380A (en) * | 2023-02-09 | 2023-04-11 | 云南国钛金属股份有限公司 | Process for co-producing ferrous chloride tetrahydrate by waste molten salt and waste acid |
| CN116216785A (en) * | 2023-01-09 | 2023-06-06 | 云南国钛金属股份有限公司 | Method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag |
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