CN114105759A - Method for synthesizing long-strip-shaped ferrous oxalate from hematite slag in one pot - Google Patents
Method for synthesizing long-strip-shaped ferrous oxalate from hematite slag in one pot Download PDFInfo
- Publication number
- CN114105759A CN114105759A CN202110897483.XA CN202110897483A CN114105759A CN 114105759 A CN114105759 A CN 114105759A CN 202110897483 A CN202110897483 A CN 202110897483A CN 114105759 A CN114105759 A CN 114105759A
- Authority
- CN
- China
- Prior art keywords
- hematite
- pot
- slag
- ferrous oxalate
- strip
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
Abstract
The invention belongs to the technical field of hydrometallurgy slag treatment and comprehensive recovery, and particularly relates to a method for synthesizing long-strip-shaped ferrous oxalate from hematite slag in one pot. The invention innovatively adds the reducing agent in the process of leaching the hematite slag by the oxalic acid, realizes the synchronous operation of leaching the oxalic acid and reduction crystallization in one pot, further cooperates with the joint control of the temperature and the dosage proportion in the treatment process, can generate the cooperation, can unexpectedly obtain the ferrous oxalate with the special strip shape, can not block a reaction channel on the surface of the raw material, and is also beneficial to promoting the forward movement of the one-pot reaction.
Description
Technical Field
The invention belongs to the technical field of comprehensive recovery of hydrometallurgy slag, and particularly relates to a method for synthesizing ferrous oxalate by adopting hematite slag.
Background
The zinc hydrometallurgy is a smelting process selected by most zinc smelting enterprises in China, and a large amount of zinc-containing leaching residues are generated in the production process regardless of the conventional method and the hot acid deferrization method. However, since iron in the calcine enters the solution together with zinc during hot acid leaching, iron ions in the zinc solution need to be removed subsequently to ensure the quality of the zinc solution. The iron precipitation process can be roughly divided into jarosite method, goethite method, hematite method and the like according to different iron removal methods. The hematite method has the advantages of low slag rate, good comprehensive utilization effect of raw materials, high metal recovery rate, suitability for processing the raw materials with high content of Au, Ag, Cu and In, and the iron content of the produced hematite slag is more than 60 percent. However, the hematite slag obtained by removing iron by the hematite method still contains about 4.1% of S and has certain corrosivity, so that the hematite slag is difficult to be directly used for iron making. At present, the treatment of hematite slag is mainly low-value utilization of outsourcing cement plants or iron and steel plants, and the like, so how to treat hematite slag generated in the zinc smelting process in a harmless and high-value way is an important environmental protection subject facing the current nonferrous metallurgy industry.
Ferrous oxalate is a main raw material required by nano magnetic materials, porous materials for supercapacitors and lithium iron phosphate anode materials for lithium batteries. The crystal form, the composition of hydrated ions and the purity of the lithium iron phosphate have great influence on the performance of the synthetic lithium iron phosphate. At present, iron sources for preparing the lithium iron phosphate anode material mainly comprise ferrous oxalate and ferric phosphate. However, the existing ferrous oxalate is generally prepared by analytically pure raw materials, and the ferrous oxalate is expensive.
In the prior art, a technology for preparing high-valued ferrous oxalate by taking hematite slag as an iron source does not exist.
Disclosure of Invention
Aiming at the problem that the high-value production of the ferrous oxalate by the hematite slag is not realized in the industry, the invention provides a method for converting the hematite slag into the ferrous oxalate by one step by adopting a dissolving recrystallization method, aiming at realizing the one-pot preparation of the ferrous oxalate under the mild condition, improving the conversion rate of one-pot reaction and solving the problem of low-value utilization of the hematite slag.
The invention aims to provide a technical concept of preparing ferrous oxalate by one pot of hematite slag, however, researches find that the successful implementation of the technical concept needs to solve the technical problems that ferrous oxalate precipitates continuously synthesized in the one pot preparation process are attached to the surface of unreacted hematite slag to block a reaction channel, so that the reaction conversion rate is low, the product purity is low and the like, and the invention provides the following technical scheme through deep research aiming at the technical problems faced by the one pot synthesis:
a method for synthesizing long-strip-shaped ferrous oxalate from hematite slag in one pot comprises the steps of synchronously adding oxalic acid and a reducing agent into slurry of the hematite slag, carrying out one-pot reaction at the temperature of more than or equal to 40 ℃ after mixing, and then separating to obtain the ferrous oxalate with a long-strip-shaped appearance.
According to research, the invention discovers that a reducing agent is innovatively added in the oxalic acid leaching process, so that one pot of oxalic acid leaching and reduction crystallization is synchronously performed, the cooperation is further realized by matching the joint control of the temperature and the dosage proportion in the treatment process, the synergy can be generated, the ferrous oxalate with a special strip shape can be obtained unexpectedly, the reaction channel on the surface of the raw material can not be blocked, and the forward movement of one pot reaction can be promoted. According to the invention, one-pot synchronization of oxalic acid and a reducing agent and cooperative control of temperature and proportion can be realized, the long-strip-shaped ferrous oxalate can be synthesized from hematite slag in one pot under normal pressure and mild conditions, and the one-pot conversion rate and the product purity can be improved. The method takes the hematite slag as a raw material to prepare the battery precursor ferrous oxalate dihydrate, has simple preparation process and high purity of the produced product, can fully utilize the hematite slag and can realize low-cost industrial production of the ferrous oxalate dihydrate.
In the invention, the solvent in the slurry is water;
preferably, in the slurry, the mass ratio of the solvent to the hematite slag is 16: 1-40: 1.
in the invention, the one-pot synchronous use of the oxalic acid and the reducing agent and the combined control of the temperature and the proportion are the keys for synergistically improving the conversion rate and the purity of the raw materials and the shape of the long strip.
In the invention, the ore pulp containing the oxalic acid and the reducing agent is synchronously added into the hematite slag. For example, a mixed solution containing oxalic acid and a reducing agent may be added to a slurry of hematite slag.
In the invention, the reducing agent is ascorbic acid.
In the present invention, the weight ratio of the reducing agent to the hematite slag (dry weight basis) is greater than or equal to 1, preferably 1-2: 1.
in the invention, the oxalic acid is not lower than the theoretical amount of the complete reaction of the iron in the hematite slag;
preferably, the weight ratio of oxalic acid to hematite residue (dry basis) is greater than or equal to 1.5: 1; more preferably 1.5 to 2.5: 1.
in the invention, a one-pot reaction is carried out under an open condition;
preferably, the one-pot reaction is carried out under stirring, and the preferred stirring speed is 100-350 r/min.
In the invention, the temperature of the one-pot reaction is preferably 40-60 ℃.
Preferably, the time of the one-pot reaction is greater than or equal to 2 h; further preferably 2 to 4 hours.
According to the invention, after one-pot reaction, solid-liquid separation is carried out, and then washing, alcohol washing and drying treatment are carried out to obtain the ferrous oxalate with the strip-shaped morphology.
A preferred method of the invention comprises the steps of:
(1): adding hematite slag into water, wherein the mass ratio of a solvent to the hematite slag is (16: 1) - (40): 1; stirring for 5-10 min;
(2): synchronously adding a reducing agent and a leaching agent into the hematite slag-solvent system, wherein the mass ratio of the reducing agent (ascorbic acid) to the leaching agent to the hematite slag is 1-2: 1.5-2.5: 1; uniformly mixing and stirring the mixed system, and reacting at the temperature of 40-60 ℃ for 2-4 h to obtain a reaction product; the reaction conditions are all normal pressure air atmosphere.
(3): washing the product obtained after the reaction in the step (2) for 3-5 times by using distilled water or absolute ethyl alcohol, and drying the washed product in a freezing vacuum manner or in a vacuum oven to obtain a dried product;
the method can also be extended to the preparation application of other similar materials. For example, a composition containing Fe2O3Replacing the hematite residue with other materials.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
in order to solve the technical problems of low conversion rate, low product purity and the like caused by the blockage of a reaction channel in the reaction process in the process of preparing the ferrous oxalate from the hematite by one pot, the invention can unexpectedly obtain the ferrous oxalate with a strip shape by synchronously cooperating the oxalic acid and the reducing agent by one pot and further cooperating with the joint control of the reaction temperature and the material proportion, can not seal the reaction channel, can effectively promote the forward movement of the reaction, and can improve the conversion rate and the product purity. Through the cooperative control of the means, the invention can obtain the raw material conversion rate of about 95 percent, and in addition, the product has good uniform strip shape and high purity.
The whole reaction is carried out in the air atmosphere at normal temperature and normal pressure, the reaction condition is mild, the operation is simple, the harmless low-cost treatment and value-added utilization of the hematite slag are realized, and the industrial application prospect is wide.
The method has the advantages that the hematite slag can be utilized in a large scale and high value mode, so that the environmental risk is eliminated, and the high value resource utilization of the hematite slag is realized.
Drawings
FIGS. 1 and 2 are XRD and SEM images, respectively, of hematite slag;
FIGS. 3 and 4 are XRD and SEM images, respectively, of the product obtained in example 1;
FIG. 5 is an SEM of the product obtained in example 2 (2: 1 for the left image; 2.5:1 for the right image);
FIG. 6 is an SEM of the product obtained in example 3 (2: 1 by weight);
FIG. 7 is an SEM photograph of the product obtained in example 4 (temperature 50 ℃);
FIGS. 8 and 9 are an XRD pattern and an SEM pattern, respectively, of the product obtained in comparative example 1;
FIGS. 10 and 11 are XRD patterns of the product of comparative example 2, respectively;
fig. 12 and 13 are SEM and XRD charts of the product obtained in comparative example 3.
FIG. 14 is an XRD pattern of the products obtained in comparative example 4 and comparative example 5;
FIG. 15 is an SEM photograph of the product obtained in comparative example 6.
Detailed Description
The present invention will be described in further detail with reference to examples.
The hematite slag in the embodiment of the invention is hematite slag generated by a hematite iron removal method in a zinc hydrometallurgy process, wherein the iron content percentage is 77.1%.
TABLE 1 content of major elements of hematite slag and water bath product ferrous oxalate
| Element (%) | Fe | O | S | As | Zn | Ca | Al | K |
| Hematite slag | 77.1 | 16.4 | 4.1 | 0.8 | 0.4 | 0.3 | 0.2 | 0.2 |
| Ferrous oxalate | 79.9 | 19.3 | 0.5 | / | 0.5 | 0.04 | 0.04 | 0.04 |
Example 1
In this example, the method for synthesizing ferrous oxalate dihydrate by using hematite slag (XRD is shown in fig. 1, and SEM is shown in fig. 2) generated by zinc smelting is performed according to the following steps:
(1) adding 3g of hematite slag into solvent water, and uniformly stirring to obtain slurry, wherein the mass ratio of the solvent water to the hematite slag is 16: 1;
(2) synchronously adding a leaching agent oxalic acid and a reducing agent ascorbic acid (adding a mixed solution of oxalic acid and ascorbic acid) into the slurry obtained in the step (1); the mass ratio of the leaching agent to the reducing agent to the hematite slag is 1.5: 1:1, uniformly mixing to obtain a precursor system;
(3) stirring the precursor system at 60 ℃ (the stirring speed is 250r/min) for reaction, carrying out the reaction process in an open container for 2h, washing with distilled water or absolute ethyl alcohol after the reaction, pouring out supernatant, and repeating for 3 times to obtain a reaction product;
(4) and (4) drying the reaction product obtained in the step (3) in air or adopting vacuum freeze drying to obtain light yellow product powder. The XRD and SEM patterns of the reaction product are shown in figure 3 and figure 4. The research finds that the product has uniform and specific long strip shape and excellent crystal phase purity, and the product has excellent conversion rate (the conversion rate of raw materials is 96 percent in terms of iron) and has excellent industrial value.
Example 2
Compared with example 1, the difference is only that the ratio of oxalic acid is changed, wherein the weight ratio of the oxalic acid to the hematite is (a) 2: 1; (b) 2.5:1 (the amount of hematite slag used was the same as in example 1).
The treated products were found by measurement to have a morphology similar to the elongated structure of example 1. The SEM image is shown in FIG. 5 (the left image is the case a; the right image is the case b), and the conversion rates of the raw materials are respectively 96% and 97% in terms of iron.
Example 3
Compared with example 1, the difference is only that the ratio of ascorbic acid is changed, wherein the weight ratio of ascorbic acid to hematite residue is respectively: (a) 1.5: 1; (b) 2:1 (the amount of hematite slag is the same as that in example 1);
the treated products were found by measurement to have a morphology similar to the elongated structure of example 1. For example, the SEM image of the group a experiment is shown in fig. 6. The conversion of the raw material was 95% and 96% based on iron, respectively.
Example 4
The difference from example 1 was only that the reaction temperature in step (3) (one-pot reaction temperature) was changed to 50 ℃ and 40 ℃.
The treated products were found by measurement to have a morphology similar to the elongated structure of example 1. For example, the SEM image of the 50 ℃ product is shown in FIG. 7. The conversion of the raw material was 95% and 96% based on iron, respectively.
Comparative example 1
Compared with the embodiment 1, the difference is that one-pot synchronous treatment of oxalic acid and a reducing agent is not carried out, and the specific operation is as follows:
(1) 3g of hematite slag (same as example 1) is added into solvent water and stirred uniformly to obtain slurry, wherein the mass ratio of the solvent water to the hematite slag is 16: 1;
(2) adding oxalic acid serving as a leaching agent into the slurry obtained in the step (1), wherein the mass ratio of the leaching agent to the hematite slag is 1.5:1, the reaction temperature is 60 ℃, the leaching time is 2 hours, and uniformly mixing to obtain a precursor system;
(3) adding ascorbic acid (the mass ratio of the ascorbic acid to the hematite slag is 1:1) into the leachate obtained in the step (2), washing the leachate by using distilled water or absolute ethyl alcohol after reaction, pouring out supernate, and repeating the washing for 3 times to obtain a reaction product;
(4) and (4) drying the reaction product obtained in the step (3) in air or adopting vacuum freeze drying, and putting the dried sample into a mortar for grinding to obtain light yellow product powder. The XRD pattern and SEM pattern distribution of the product are shown in figures 8 and 9. The main component of the leaching slag is ferric oxide, and the conversion rate of the hematite slag to the ferrous oxalate is lower and is 65 percent. Therefore, the material with special morphology can be obtained through the one-pot leaching synchronous crystallization treatment, and the conversion rate is improved.
Comparative example 2
The only difference compared to example 1 is that the ascorbic acid content is reduced, i.e. the ratio of ascorbic acid to hematite residue is controlled to be 1: 5 and 1: 3 (the amount of hematite slag used was the same as in example 1).
XRD patterns of this case are shown in FIG. 10 (1: 5 ratio of ascorbic acid: hematite) and FIG. 11 (1: 3 ratio of ascorbic acid: hematite), and the results show that the product also contains Fe2O3Phase, which shows that the amount of reducing agent added is small and Fe is hardly promoted2O3Completely converted into ferrous oxalate dihydrate. It can be seen that the purity of the crystalline phase of the product is poor without control within the claimed range.
Comparative example 3
The only difference compared to example 1 is that the amount of oxalic acid is reduced, i.e. the ratio of oxalic acid to hematite residue is controlled to 1: 3 (the amount of hematite slag used was the same as in example 1).
The SEM image and XRD of this case are shown in fig. 12 and 13, respectively, fig. 12 showing that this case does not form the long-stripe morphology material of the present invention, and fig. 13 showing that the product is also poor in crystallinity.
Comparative example 4
The only difference compared to example 1 is that in step (2), ascorbic acid alone and oxalic acid alone are not added.
XRD of this case is shown in FIG. 14, without formation of the material of the present invention, the major phase in the product is still Fe compared to the original hematite residue2O3。
Comparative example 5
The only difference compared to example 1 is that in step (2), only oxalic acid is added, and ascorbic acid is not added.
XRD of this case is shown in FIG. 14, and the main phase in the product is Fe2O3The material of the present invention is not formed.
Comparative example 6
The only difference compared to example 1 is that the reaction temperature is ambient (25 deg.C), the SEM of this case is shown in FIG. 15, and the material with the morphology described in the present invention is not formed.
Claims (10)
1. A method for synthesizing long-strip-shaped ferrous oxalate from hematite slag in one pot is characterized in that oxalic acid and a reducing agent are added into ore pulp of the hematite slag, the mixture is subjected to one-pot reaction at the temperature of more than or equal to 40 ℃, and then the ferrous oxalate with a long-strip-shaped appearance is obtained through separation;
wherein, the reducing agent and the oxalic acid are both more than or equal to the theoretical amount of complete reaction of the hematite slag.
2. The method of one-pot synthesis of ferrous oxalate from hematite residue as claimed in claim 1 wherein said reducing agent is ascorbic acid.
3. The method for synthesizing long-strip-shaped ferrous oxalate from hematite slag in one pot according to claim 1, wherein the weight ratio of the reducing agent to the hematite slag is greater than or equal to 1, preferably 1-2: 1.
4. the method for one-pot synthesis of elongated ferrous oxalate from hematite slag as claimed in claim 1 wherein the weight ratio of oxalic acid to hematite slag is greater than or equal to 1.5:1, preferably 1.5-2.5: 1.
5. the method of one-pot synthesis of elongated ferrous oxalate from hematite slag as set forth in claim 1 wherein a slurry of hematite slag is simultaneously added with an iron containing acid and a reducing agent.
6. The method of one-pot synthesis of ferrous oxalate from hematite slag as claimed in claim 1 wherein the solvent in the slurry is water;
preferably, in the slurry, the mass ratio of the solvent to the hematite slag is 16: 1-40: 1.
7. the method of one-pot synthesis of ferrous oxalate from hematite residue as claimed in claim 1 wherein the one-pot reaction is carried out under open conditions;
preferably, the one-pot reaction is carried out under stirring, and the preferred stirring speed is 100-350 r/min.
8. The method for one-pot synthesis of ferrous oxalate from hematite slag as claimed in claim 1, wherein the temperature of the one-pot reaction is 40-60 ℃;
preferably, the one-pot reaction time is 2-4 h.
9. The method for one-pot synthesis of long-strip-shaped ferrous oxalate from hematite slag according to claim 1, wherein after one-pot reaction, solid-liquid separation is carried out, and then the treatment of water washing, alcohol washing and drying is carried out to obtain the long-strip-shaped ferrous oxalate.
10. The process of claim 1, wherein the hematite residue is obtained from hematite oreThe method for synthesizing long-strip-shaped ferrous oxalate in one pot is characterized by adopting a method containing Fe2O3Replacing the hematite residue with other materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110897483.XA CN114105759B (en) | 2021-08-05 | 2021-08-05 | Method for synthesizing long-strip-shaped ferrous oxalate from hematite slag in one pot |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110897483.XA CN114105759B (en) | 2021-08-05 | 2021-08-05 | Method for synthesizing long-strip-shaped ferrous oxalate from hematite slag in one pot |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114105759A true CN114105759A (en) | 2022-03-01 |
| CN114105759B CN114105759B (en) | 2022-09-13 |
Family
ID=80440961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110897483.XA Active CN114105759B (en) | 2021-08-05 | 2021-08-05 | Method for synthesizing long-strip-shaped ferrous oxalate from hematite slag in one pot |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114105759B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043722A (en) * | 2022-06-23 | 2022-09-13 | 中南大学 | Method for recovering iron resource in iron-containing waste residues of zinc hydrometallurgy |
| CN115466174A (en) * | 2022-08-26 | 2022-12-13 | 重庆文理学院 | Method for preparing ferrous oxalate by efficiently utilizing red mud |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085732A (en) * | 2007-07-12 | 2007-12-12 | 中国铝业股份有限公司 | Method for producing ferrous oxalate from hematite |
| CN102336646A (en) * | 2010-07-21 | 2012-02-01 | 宁波杉杉新材料科技有限公司 | Preparation method of ferrous oxalate |
| CN111153790A (en) * | 2019-12-31 | 2020-05-15 | 河北中科同创科技发展有限公司 | Preparation method of ferrous oxalate dihydrate |
| CN112340918A (en) * | 2020-11-11 | 2021-02-09 | 山东云水环保科技有限公司 | Method for recycling steel pickling rust removal waste liquid |
-
2021
- 2021-08-05 CN CN202110897483.XA patent/CN114105759B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085732A (en) * | 2007-07-12 | 2007-12-12 | 中国铝业股份有限公司 | Method for producing ferrous oxalate from hematite |
| CN102336646A (en) * | 2010-07-21 | 2012-02-01 | 宁波杉杉新材料科技有限公司 | Preparation method of ferrous oxalate |
| CN111153790A (en) * | 2019-12-31 | 2020-05-15 | 河北中科同创科技发展有限公司 | Preparation method of ferrous oxalate dihydrate |
| CN112340918A (en) * | 2020-11-11 | 2021-02-09 | 山东云水环保科技有限公司 | Method for recycling steel pickling rust removal waste liquid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043722A (en) * | 2022-06-23 | 2022-09-13 | 中南大学 | Method for recovering iron resource in iron-containing waste residues of zinc hydrometallurgy |
| CN115043722B (en) * | 2022-06-23 | 2024-01-26 | 中南大学 | Method for recovering iron resources in iron-containing waste residues of zinc hydrometallurgy |
| CN115466174A (en) * | 2022-08-26 | 2022-12-13 | 重庆文理学院 | Method for preparing ferrous oxalate by efficiently utilizing red mud |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114105759B (en) | 2022-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114105759B (en) | Method for synthesizing long-strip-shaped ferrous oxalate from hematite slag in one pot | |
| CN102251119B (en) | Method for recycling vanadium extraction tailings | |
| CN102557050B (en) | New process for comprehensively utilizing potassium feldspar | |
| CN101817561B (en) | Method for pollution-free production of sodium chromate by pressure leaching of chromite | |
| CN101508471B (en) | Process for producing cobaltic-cobaltous oxide | |
| CN109536732B (en) | Method for preparing ternary precursor material by recycling copper sulfide slag | |
| CN110872107A (en) | Method for recovering iron from alloy leaching solution in cobalt-nickel industry | |
| CN104946903A (en) | Method for recovering metal resource from zinc calcine through reduction roasting-leaching-zinc sinking | |
| CN115140777B (en) | Method for producing ferromanganese composite material for soft magnetic by utilizing ocean manganese nodule | |
| CN109880999B (en) | Method for recovering iron in copper slag after modification of composite additive and application | |
| CN102994746B (en) | Method for producing nickel sulfide ore concentrate by use of industrial waste acid | |
| CN110129587A (en) | A kind of method that spodumene vacuum metling extracts lithium metal and prepares alusil alloy | |
| CN112570419A (en) | Aluminum ash recycling method, harmless aluminum ash and application of harmless aluminum ash | |
| WO2023045331A1 (en) | Method for selectively recovering valuable metal in waste lithium battery | |
| EP3276014B1 (en) | Cobalt powder production method | |
| US11791078B1 (en) | Method for synchronous production of manganese tetraoxide and ferric oxide for soft magnetic material by using marine polymetallic nodules | |
| CN114906830B (en) | Method for controllably preparing battery-grade iron phosphate from pyrite cinder | |
| CN103074496B (en) | Method for separating and purifying magnesium dioxide from anode mud | |
| CN102718267B (en) | Method for preparing black iron oxide by utilizing yellow ammonium iron alum slag | |
| CN107902925A (en) | The method of light magnesium oxide is smelted using magnesite | |
| CN113912131B (en) | Zinc ferrite treatment method | |
| CN104099478B (en) | A kind of method reclaiming and prepare chromium metal | |
| CN103441315B (en) | Method for preparing manganese-zinc ferrite soft magnet by taking biological leachate of waste zinc-manganese battery as raw material | |
| CN113930621B (en) | Treatment method for reducing and recycling jarosite slag | |
| CN115448273B (en) | Method for preparing lithium dihydrogen phosphate by taking lepidolite as raw material |
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 |