CN105692576A - Method for preparing battery-grade FePO4 from industrial iron-containing waste - Google Patents
Method for preparing battery-grade FePO4 from industrial iron-containing waste Download PDFInfo
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- CN105692576A CN105692576A CN201610134686.2A CN201610134686A CN105692576A CN 105692576 A CN105692576 A CN 105692576A CN 201610134686 A CN201610134686 A CN 201610134686A CN 105692576 A CN105692576 A CN 105692576A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5805—Phosphides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a method for preparing battery-grade FePO4 from industrial iron-containing waste. The method comprises steps as follows: iron-containing waste acid is taken and filtered, and waste iron residues are added to a filtrate and react at 30-35 DEG C for 24-48 h until the pH of a solution is 5-6; the solution is filtered 1-3 times, a green settled solution is obtained, hydrogen peroxide and a phosphorous source are added under the stirring condition, and the solution is subjected to a reaction for 12-18 h; the solution is heated to 85-95 DEG C in a water bath, the phosphorus source and a sodium hydroxide solution are added, the solution is subjected to a reaction for 3-6 h, and a yellow suspension is produced; the yellow suspension is filtered, washed and dried, and battery-grade FePO4, namely, FePO4*2H2O, is obtained and is in a regular sheet shape. The FePO4 is synthesized at the low temperature; no impurities are produced during synthesis, and pure-phase FePO4*2H2O can be obtained. The prepared FePO4*2H2O has stable properties, and all indexes meet the requirement of battery-grade FePO4.
Description
Technical field
The present invention relates to a kind of LITHIUM BATTERY phosphate dihydrate ferrum and preparation method thereof, this battery-grade iron phosphate is the desirable feedstock preparing lithium ion battery anode material lithium iron phosphate, belongs to technical field of energy material preparation。
Background technology
The energy is that human society is rely the basis and the driving source of all development that exist, progress along with science and technology, the mankind become increasingly dependent on the energy, coal, oil, natural gas etc. are successively developed as the energy, these non-renewable energy resources are to generate in the development evolvement of the earth, cycle is very long, and the mankind rob formula exploitation makes these non-renewable energy resources progressively face exhaustion。Although wind energy, solar energy are inexhaustible novel renewable energy, but these energy are largely subject to the impact of natural environment, are discontinuous in energy form, it will be made to obtain Appropriate application and be necessary for by all kinds of Novel energy storage apparatus。Wherein, chemical energy source is one of important energy storage device, has the features such as energy conversion efficiency height, energy density are high, removable。Chemical energy source experienced by from once to secondary, from aqueous solution to organic solution system, and a series of technical revolution such as from liquid electrolyte to all solid state electrolyte。Traditional secondary cell such as plumbic acid, Ni-MH battery, nickel-cadmium cell, because of its environmental pollution, open-circuit voltage is low, energy density is little, service life is short, have the shortcomings such as memory effect, self-discharge rate are big, can not meet people's needs to secondary cell performance。Lithium ion battery is with voltage platform high (>=3V), and specific energy is big, and self discharge is little, has extended cycle life, memory-less effect, and polluting the advantage such as little becomes the first-selection of present energy-storage battery。
Olivine structure lithium iron phosphate (LiFePO4) since within 1997, being found by Goodenough etc. just because of advantages such as it are safe and environment-friendly, specific capacity is high, cycle performance is excellent, hot properties is good, be described as anode material for lithium-ion batteries most with prospects。Long cycle life, excellent high-rate discharge ability, high discharge platform, big energy density and good thermal stability, also make LiFePO4 become the preferred material of high power power battery anode。But, LiFePO4 there is also the shortcomings such as electronic conductivity is relatively low, lithium ion diffusion coefficient is little, tap density is not high, thus governs its application and development。At present, the electronic conductivity of LFP and the transmission of lithium ion is improved by Surface coating conductive materials；Metal ion mixing is adopted to improve the electric conductivity of material from inside；The tap density of material is promoted by adjusting and controlling the size of granule, pattern, distribution etc.。
Present stage, LiFePO4The specific capacity that major problem is that under high magnification of material is too low, and this is owing to material itself surveys electronic conductivity and lithium ion at FePO4/LiFePO4Between biphase, diffusion rate causes slowly。The synthesis condition of electrode material and electrochemical characteristic depend primarily on presoma, and raw material of good performance can provide better chemical property for LiFePO 4 material。Use Ferrox. (or iron sesquioxide) as source of iron, phosphoric acid (or ammonium phosphate, ammonium dihydrogen phosphate, diammonium phosphate) is widely used as the technology path of phosphorus source, but the source of iron of this technology path derives from raw material two kinds different with phosphorus source, relatively costly especially with Ferrox., and make troubles using its control being also easy in product residual carbon content as source of iron。For this, existing many enterprises adopt iron phosphate as raw material, enormously simplify LiFePO4The synthesis technique of material。
At present, the preparation technology of iron phosphate is varied, as: coprecipitation, hydro-thermal method etc.。Wherein, it is make hydrated ferric oxide. again after metallic iron is made iron salt mostly, prepares iron phosphate by hydrated ferric oxide. and phosphatase reaction, or utilize iron salt and phosphate generation metathesis reaction to prepare iron phosphate, and adopt ammonia to regulate the pH value of reaction system more。Cost of material in these preparation technologies is all higher, and in contrast, the present invention adopts industrial ferrous contained garbage to be that raw material synthesizes, not only with low cost, and solves the process of iron-contained waste material, plays the effect of environmental protection, saving。
Summary of the invention
It is an object of the invention to provide the green of a kind of battery-grade iron phosphate, environmental protection synthetic method。Specific as follows:
A kind of method utilizing industrial ferrous contained garbage to prepare battery-grade iron phosphate, comprises the steps:
(1) take ferrous waste acid, in filtrate, add Waste iron slag after filtration, at 30～35 DEG C of temperature, react 24～48h, be 5～6 to pH value of solution；
(2) above-mentioned solution is filtered 1～3 time, obtain green settled solution, under stirring condition, be separately added into hydrogen peroxide and phosphorus source, react 12～18h；
(3) again by above-mentioned solution through heating in water bath to 85～95 DEG C, add phosphorus source and sodium hydroxide solution, react 3～6h, generate yellow suspension；
(4) yellow suspension is through filtering, wash, drying, and obtains battery-grade iron phosphate, and this battery-grade iron phosphate is phosphate dihydrate ferrum FePO4·2H2O, its pattern is the lamellar of rule。
Described ferrous waste acid includes processing the spent acid produced in iron and steel or electroplating process, and wherein in ferrous waste acid, concentration of hydrochloric acid is 180～220g/L；Described Waste iron slag includes waste iron filing, scrap iron block or scrap iron mud。
Phosphorus source described in step (2) includes phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate or diammonium phosphate；Sodium hydroxide can also be ammonia。
The purity of hydrogen peroxide is 30%, and the purity of phosphoric acid is 85%, and the purity of ammonium phosphate, ammonium dihydrogen phosphate and diammonium phosphate is all higher than 98%, and the mass concentration of ammonia is 25%～28%, and the molar concentration of sodium hydroxide is 1～5mol/L。
In step (1), ferrous waste acid is 30-70:1-4 with the weight ratio of the addition of Waste iron slag；In step (2), hydrogen peroxide is 7～9:9～11 with the volume ratio of the addition of phosphorus source；The volume ratio of the addition of step (3) phosphorus source and sodium hydroxide solution is 10～15:5～30；In step (6), baking temperature is 80～120 DEG C, and drying time is 8～12h。
More preferably in step (1), the volume of ferrous waste acid is 400～600mL, and the addition of Waste iron slag is 15～25g；In step (2), the addition of hydrogen peroxide and phosphoric acid is respectively as follows: 70～90mL and 90～110mL；The addition of step (3) phosphoric acid and sodium hydroxide solution is respectively as follows: 100～150mL and 50～300mL；In step (6), baking temperature is 100 DEG C, and drying time is 10h。
The method utilizing industrial ferrous contained garbage synthesis battery-grade iron phosphate of the present invention has the advantage that
(1) synthesize with two kinds of industrial ferrous contained garbages (i.e. ferrous waste acid and Waste iron slag) for raw material, not only effectively reduce the synthesis cost of iron phosphate, but also reduce the pollution of trade waste substantially, promote its commercial value further；
(2) building-up process of the iron phosphate that the present invention relates to carries out under low temperature (100 DEG C), low for equipment requirements, it is easy to realize commercial production；
(3) building-up process does not produce any impurity, the phosphate dihydrate ferrum of pure phase can be obtained, be prone to keep the concordance of material between different batches simultaneously；
(4) the phosphate dihydrate ferrum stable in properties that prepared by the present invention, indices all reaches the requirement of battery-grade iron phosphate, is the desirable feedstock preparing LiFePO4。
LITHIUM BATTERY phosphate dihydrate ferrum (FePO prepared by the present invention4·2H2O) there is following distinguishing feature:
(1) Sample crystals structure is monocline, and space group is P21/ n, and it is absent from any impurity, present the sheet-like morphology of rule；
(2) properties of samples is stable, it is easy to preserve, and different batches gained sample can keep the concordance of height；
(3) the ferrum phosphorus ratio of sample is in 0.95～1.03 scope, meets the commercialization requirement of battery-grade iron phosphate；
(4) LiFePO4 being Material synthesis with this material shows the chemical property of excellence。
Accompanying drawing explanation
Fig. 1 is embodiment 1 sample F ePO4·2H2The XRD figure spectrum of O。
Fig. 2 is embodiment 1 sample F ePO4·2H2The SEM photograph of O。
Fig. 3 is embodiment 1 sample LiFePO4The charging and discharging curve of/C。
Fig. 4 is embodiment 1 sample LiFePO4The cycle performance curve of/C。
Detailed description of the invention
Embodiment 1
Take 500mL ferrous waste acid, after filtration, gained solution will add 20g Waste iron slag, and at 30 DEG C of temperature, react 48h, to pH value of solution=5。Subsequently, above-mentioned solution is filtered 2 times, obtain green settled solution；Under stirring condition, respectively 80mL hydrogen peroxide and 100mL phosphoric acid are added reaction 18h in above-mentioned settled solution。Finally, when heating in water bath is to 92 DEG C, adds 110mL phosphoric acid and 250mL sodium hydroxide solution, after reaction 5h, generate yellow suspension；At 100 DEG C, dry 10h when filtration, washing are to pH=6, obtain phosphate dihydrate ferrum (FePO4·2H2O) sample。
Accurately weigh Li2CO3、FePO4·2H2O (embodiment 1) and glucose ball milling 12h in anhydrous ethanol medium, is transferred in the baking oven of 50 DEG C and dries about 12h after mixing, sinter, sieve, obtain sample LiFePO after to be dried in tube furnace under nitrogen atmosphere4/ C。By active substance LiFePO4/ C and acetylene black, Kynoar (PVdF), by the mass ratio of 8:1:1 furnishing slurry in N-Methyl pyrrolidone (NMP) medium, are coated on aluminium foil, through super-dry, rush film and press mold makes working electrode。With metallic lithium foil for electrode, Celgard2400 is barrier film, 1MLiPF6/ (EC+DMC) (1:1) is assembled into battery for electrolyte and carries out constant current charge-discharge test, and voltage range is between 2.5～4.2V。Material is under 1C, and discharge capacity is 132.3mAh/g first, and after 100 times circulate, discharge capacity is still maintained at 112.2mAh/g, and capability retention reaches 85%。
Embodiment 2
Take 500mL ferrous waste acid, after filtration, gained solution will add 20g Waste iron slag, and at 30 DEG C of temperature, react 48h, to pH value of solution=5。Subsequently, above-mentioned solution is filtered 2 times, obtain green settled solution；Under stirring condition, respectively 80mL hydrogen peroxide and 100mL phosphoric acid are added reaction 18h in above-mentioned settled solution。Finally, when heating in water bath is to 87 DEG C, adds 110mL phosphoric acid and 250mL sodium hydroxide solution, after reaction 5h, generate yellow suspension；At 100 DEG C, dry 10h when filtration, washing are to pH=6, obtain phosphate dihydrate ferrum (FePO4·2H2O) sample。
Embodiment 3
Take 500mL ferrous waste acid, after filtration, gained solution will add 20g Waste iron slag, and at 30 DEG C of temperature, react 48h, to pH value of solution=5。Subsequently, above-mentioned solution is filtered 2 times, obtain green settled solution；Under stirring condition, respectively 80mL hydrogen peroxide and 100mL phosphoric acid are added reaction 18h in above-mentioned settled solution。Finally, when heating in water bath is to 92 DEG C, adds 80g ammonium dihydrogen phosphate and 250mL sodium hydroxide solution, after reaction 5h, generate yellow suspension；At 100 DEG C, dry 10h when filtration, washing are to pH=6, obtain phosphate dihydrate ferrum (FePO4·2H2O) sample。
Embodiment 4
Take 500mL ferrous waste acid, after filtration, gained solution will add 20g Waste iron slag, and at 30 DEG C of temperature, react 48h, to pH value of solution=5。Subsequently, above-mentioned solution is filtered 2 times, obtain green settled solution；Under stirring condition, respectively 80mL hydrogen peroxide and 100mL phosphoric acid are added reaction 18h in above-mentioned settled solution。Finally, when heating in water bath is to 92 DEG C, adds 100g ammonium dihydrogen phosphate and 250mL sodium hydroxide solution, after reaction 5h, generate yellow suspension；At 100 DEG C, dry 10h when filtration, washing are to pH=6, obtain phosphate dihydrate ferrum (FePO4·2H2O) sample。
Embodiment 5
Take 500mL ferrous waste acid, after filtration, gained solution will add 20g Waste iron slag, and at 30 DEG C of temperature, react 48h, to pH value of solution=5。Subsequently, above-mentioned solution is filtered 2 times, obtain green settled solution；Under stirring condition, respectively 80mL hydrogen peroxide and 100mL phosphoric acid are added reaction 18h in above-mentioned settled solution。Finally, when heating in water bath is to 92 DEG C, adds 150g ammonium dihydrogen phosphate and 250mL sodium hydroxide solution, after reaction 5h, generate yellow suspension；At 100 DEG C, dry 10h when filtration, washing are to pH=6, obtain phosphate dihydrate ferrum (FePO4·2H2O) sample。
Embodiment 6
Take 500mL ferrous waste acid, after filtration, gained solution will add 20g Waste iron slag, and at 30 DEG C of temperature, react 48h, to pH value of solution=5。Subsequently, above-mentioned solution is filtered 2 times, obtain green settled solution；Under stirring condition, respectively 80mL hydrogen peroxide and 100mL phosphoric acid are added reaction 18h in above-mentioned settled solution。Finally, when heating in water bath is to 92 DEG C, adds 200g ammonium dihydrogen phosphate and 250mL sodium hydroxide solution, after reaction 5h, generate yellow suspension；At 100 DEG C, dry 10h when filtration, washing are to pH=6, obtain phosphate dihydrate ferrum (FePO4·2H2O) sample。
Embodiment 7
Take 500mL ferrous waste acid, after filtration, gained solution will add 20g Waste iron slag, and at 30 DEG C of temperature, react 48h, to pH value of solution=5。Subsequently, above-mentioned solution is filtered 2 times, obtain green settled solution；Under stirring condition, respectively 80mL hydrogen peroxide and 100mL phosphoric acid are added reaction 18h in above-mentioned settled solution。Finally, when heating in water bath is to 92 DEG C, adds 250g ammonium dihydrogen phosphate and 250mL sodium hydroxide solution, after reaction 5h, generate yellow suspension；At 100 DEG C, dry 10h when filtration, washing are to pH=6, obtain phosphate dihydrate ferrum (FePO4·2H2O) sample。
Claims (6)
1. one kind utilizes the method that industrial ferrous contained garbage prepares battery-grade iron phosphate, it is characterised in that comprise the steps:
(1) take ferrous waste acid, in filtrate, add Waste iron slag after filtration, at 30～35 DEG C of temperature, react 24～48h, be 5～6 to pH value of solution；
(2) above-mentioned solution is filtered 1～3 time, obtain green settled solution, under stirring condition, be separately added into hydrogen peroxide and phosphorus source, react 12～18h；
(3) again by above-mentioned solution through heating in water bath to 85～95 DEG C, add phosphorus source and sodium hydroxide solution, react 3～6h, generate yellow suspension；
(4) yellow suspension is through filtering, wash, drying, and obtains battery-grade iron phosphate, and this battery-grade iron phosphate is phosphate dihydrate ferrum FePO4·2H2O, its pattern is the lamellar of rule。
2. utilize, described in claim 1, the method that industrial ferrous contained garbage prepares battery-grade iron phosphate, it is characterised in that described ferrous waste acid includes processing the spent acid produced in iron and steel or electroplating process, and wherein in ferrous waste acid, concentration of hydrochloric acid is 180-220g/L；Described Waste iron slag includes waste iron filing, scrap iron block or scrap iron mud。
3. utilize, described in claim 1, the method that industrial ferrous contained garbage prepares battery-grade iron phosphate, it is characterised in that the phosphorus source described in step (2) includes phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate or diammonium phosphate；Sodium hydroxide can also be ammonia。
4. utilize, described in claim 3, the method that industrial ferrous contained garbage prepares battery-grade iron phosphate, it is characterized in that, the purity of hydrogen peroxide is 30%, the purity of phosphoric acid is 85%, the purity of ammonium phosphate, ammonium dihydrogen phosphate and diammonium phosphate is all higher than 98%, the mass concentration of ammonia is 25%～28%, and the molar concentration of sodium hydroxide is 1～5mol/L。
5. utilize, described in claim 1, the method that industrial ferrous contained garbage prepares battery-grade iron phosphate, it is characterised in that in step (1), ferrous waste acid is 30-70:1-4 with the weight ratio of the addition of Waste iron slag；In step (2), hydrogen peroxide is 7～9:9～11 with the volume ratio of the addition of phosphorus source；The volume ratio of the addition of step (3) phosphorus source and sodium hydroxide solution is 10～15:5～30；In step (6), baking temperature is 80～120 DEG C, and drying time is 8～12h。
6. utilize, described in claim 3, the method that industrial ferrous contained garbage prepares battery-grade iron phosphate, it is characterised in that in step (1), the volume of ferrous waste acid is 400～600mL, and the addition of Waste iron slag is 15～25g；In step (2), the addition of hydrogen peroxide and phosphoric acid is respectively as follows: 70～90mL and 90～110mL；The addition of step (3) phosphoric acid and sodium hydroxide solution is respectively as follows: 100～150mL and 50～300mL；In step (6), baking temperature is 100 DEG C, and drying time is 10h。
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Cited By (15)
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| CN107317029A (en) * | 2017-06-22 | 2017-11-03 | 赣州有色冶金研究所 | A kind of preparation method of ferric phosphate |
| CN107611433A (en) * | 2017-09-19 | 2018-01-19 | 江苏荣信环保科技有限公司 | A kind of method for preparing battery-grade iron phosphate using heavy metal sewage sludge and heavy metal spent acid |
| CN107665979A (en) * | 2017-08-24 | 2018-02-06 | 浙江工业大学 | Lithium battery cathode prepared based on iron mud and preparation method thereof |
| CN108609595A (en) * | 2018-05-10 | 2018-10-02 | 湖南雅城新材料有限公司 | Ferric phosphate and its preparation method and application |
| CN110342484A (en) * | 2019-08-01 | 2019-10-18 | 湖北昊瑞新能源有限公司 | A kind of preparation method of low cost sheet ferric orthophosphate |
| CN110436428A (en) * | 2019-07-08 | 2019-11-12 | 湖南雅城新材料有限公司 | A kind of preparation method of sheet-form iron phosphate, sheet-form iron phosphate obtained and its application |
| CN110451471A (en) * | 2019-07-08 | 2019-11-15 | 湖南雅城新材料有限公司 | A kind of preparation method of ferric phosphate, ferric phosphate obtained and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107317029A (en) * | 2017-06-22 | 2017-11-03 | 赣州有色冶金研究所 | A kind of preparation method of ferric phosphate |
| CN107665979A (en) * | 2017-08-24 | 2018-02-06 | 浙江工业大学 | Lithium battery cathode prepared based on iron mud and preparation method thereof |
| CN107611433A (en) * | 2017-09-19 | 2018-01-19 | 江苏荣信环保科技有限公司 | A kind of method for preparing battery-grade iron phosphate using heavy metal sewage sludge and heavy metal spent acid |
| CN107611433B (en) * | 2017-09-19 | 2020-09-04 | 江苏荣信环保科技有限公司 | Method for preparing battery-grade iron phosphate by using heavy metal sludge |
| CN108609595A (en) * | 2018-05-10 | 2018-10-02 | 湖南雅城新材料有限公司 | Ferric phosphate and its preparation method and application |
| CN108609595B (en) * | 2018-05-10 | 2020-08-21 | 湖南雅城新材料有限公司 | Iron phosphate and preparation method and application thereof |
| CN110872107A (en) * | 2018-08-30 | 2020-03-10 | 衢州华友钴新材料有限公司 | Method for recovering iron from alloy leaching solution in cobalt-nickel industry |
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| CN111377558A (en) * | 2020-03-17 | 2020-07-07 | 航天凯天环保科技股份有限公司 | Synchronous treatment of Fenton iron mud and FePO obtaining4Resource utilization method |
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| CN113955733A (en) * | 2021-11-12 | 2022-01-21 | 斯瑞尔环境科技股份有限公司 | Method for preparing iron phosphate by using iron-containing waste hydrochloric acid |
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| CN113955732B (en) * | 2021-11-12 | 2024-04-12 | 斯瑞尔环境科技股份有限公司 | Method for preparing ferric phosphate by using ferric trichloride as catalyst |
| CN113955733B (en) * | 2021-11-12 | 2024-04-12 | 斯瑞尔环境科技股份有限公司 | Method for preparing ferric phosphate by utilizing waste hydrochloric acid containing iron |
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| CN115010185A (en) * | 2022-06-10 | 2022-09-06 | 马钢(合肥)钢铁有限责任公司 | Production method of battery-grade ferrous chloride |
| CN115959643A (en) * | 2022-12-05 | 2023-04-14 | 上海安赐环保科技股份有限公司 | Resource utilization method of byproduct phosphorus salt and byproduct iron salt in steel pickling |
| CN115959643B (en) * | 2022-12-05 | 2024-05-03 | 上海安赐环保科技股份有限公司 | Method for recycling byproduct phosphate and iron and steel pickling byproduct ferric salt |
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