CN107611433A - A kind of method for preparing battery-grade iron phosphate using heavy metal sewage sludge and heavy metal spent acid - Google Patents

A kind of method for preparing battery-grade iron phosphate using heavy metal sewage sludge and heavy metal spent acid Download PDF

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CN107611433A
CN107611433A CN201710845301.8A CN201710845301A CN107611433A CN 107611433 A CN107611433 A CN 107611433A CN 201710845301 A CN201710845301 A CN 201710845301A CN 107611433 A CN107611433 A CN 107611433A
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heavy metal
filtrate
filter residue
sewage sludge
filter
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CN107611433B (en
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邓超群
施荣标
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Jiangsu Rongxin Environmental Protection Technology Co Ltd
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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The invention discloses a kind of method for preparing battery-grade iron phosphate using heavy metal sewage sludge and heavy metal spent acid, comprise the following steps:Seven filterings, distill twice, be electrolysed and be once calcined twice.A kind of method that battery-grade iron phosphate is prepared using heavy metal sewage sludge provided by the invention, compared with traditional preparation technology, produced in the present invention without sulfur dioxide, and be free of iron oxide and chlorion in the phosphoric acid ferro-aluminum prepared, optimize aluminum phosphate iron cell fast charge effect, the content of ferric phosphate is higher, new energy materialses are converted using solid waste, solves local environment pollution problem, promote the sustainable development of Steel Wire Products Industry, lead zinc raw material, frerrous chloride and sodium hypochlorite can be prepared from heavy metal sewage sludge simultaneously, is advantageous to popularize.

Description

A kind of method for preparing battery-grade iron phosphate using heavy metal sewage sludge and heavy metal spent acid
Technical field
The invention belongs to chemical technology field, and more specifically, more particularly to one kind is given up using heavy metal sewage sludge, heavy metal The method that acid, spent acid body refuse, waste phosphoric acid prepare battery-grade iron phosphate.
Background technology
Ferric phosphate, also known as high ferric phosphate, ferric orthophosphate, molecular formula FePO4, it is a kind of white, canescence monoclinic crystal Powder.It is iron salt solutions and the salt of sodium phosphate effect, iron therein is positive trivalent.Its main application is to manufacture LiFePO4 electricity Pond material, catalyst and ceramics etc..The color of the phosphate dihydrate iron of high-purity is near-white or shallow (light) yellow-white powder, with The loss of the crystallization water, color gradually turn yellow, and pure anhydride is in yellow-white powder.Outward appearance is in ash when phosphorus is exceeded in two water thing ferric phosphates White or dull gray white;As being in dark yellow when iron is exceeded.Ferrophosphorus ratio is the index for weighing ferric phosphate quality most critical, and is determined The factor of LiFePO4 quality most critical.When substantial amounts of ferrous iron or sodium, potassium, sulfate radical, ammonium ion in ferric phosphate such as be present, Phosphate dihydrate iron rule is in furvous or canescence.Tap density:1.13~1.59g/cm3,0.75~0.97g/ of apparent density cm3.Hydrochloric acid is soluble in during heating, but is insoluble in other acid, is practically insoluble in water, acetic acid, alcohol.
One of traditional ferric phosphate preparation method is to use divalent iron salt (such as ferrous sulfate) and phosphoric acid hydrogen ammonia, phosphoric acid, ammoniacal liquor, The reactions such as hydrogen peroxide synthesize.The technical method has an inevitable accessory substance ammonium salt (ammonium sulfate), and ammonium sulfate total amount is larger And content is low, environmental protection treatment is got up cost height, and easily pollutes environment, and accessory substance value is not high.In addition, using sulfate radical as Example, when phosphoric acid iron product is used to prepare LiFePO4 as raw material, sulfate radical therein is sintered to produce sulfur dioxide, lead Cause environmental pollution.The two of traditional ferric phosphate preparation method be with pure iron and strong acid reaction generation ferric iron, then again with phosphoric acid Reaction generation ferric phosphate.The strong acid root (such as sulfate radical) that strong acid introduces, which is liable to stick to obtained ferric phosphate product surface, to be made Acidity is presented in product, therefore generally requires to reuse ammonium to adjust acid-base value, in addition, by taking sulfate radical as an example, when phosphoric acid iron product When being used to prepare LiFePO4 as raw material, sulfate radical therein is sintered to produce sulfur dioxide, cause environmental pollution.
In view of this, it is special to propose the present invention.
The content of the invention
The invention aims to solve shortcoming present in prior art, and the one kind proposed utilizes heavy metal sewage sludge The method that battery-grade iron phosphate is prepared with heavy metal spent acid.
To achieve the above object, the present invention provides following technical scheme:One kind utilizes heavy metal sewage sludge and heavy metal spent acid The method for preparing battery-grade iron phosphate, comprises the following steps:
S1, by iron oxide waste material add reactor in, and add spent acid regulation pH value, entered after stirring using filter press Row filtering, is made filter residue one and filtrate one;
S2, filter residue one in step S1 added in reactor, and add phosphoric acid and hydrochloric acid regulation pH value, adopted after stirring reaction Filtered with filter press, filter residue two and filtrate two is made;
S3, filtered after vulcanized sodium or useless sodium sulfide solution stirring reaction will be added in filtrate one, the He of filter residue three is made Filtrate three;
S4, filter residue two in step S2 added in reactor, and add running water cleaning and filtered, obtain the He of filter residue four Filtrate four, filter residue four can direct harmless emission, filtrate four can recycle as the spent acid in step S1;
Filtrate two is added in distillation still by S5 is distilled with heat steam heating, obtains residue and to steam hydrochloric acid molten Liquid, hydrochloric acid solution can recycle as the hydrochloric acid in step S2;
S6, the residue in step S5 added in reactor, and add running water, entered after stirring using filter press Row filtering, obtains filtrate five and filter residue five, filtrate five can recycle as the spent acid in step S1;
S7, the filter residue five in step S6 is transferred in reactor, and adds pure water, filter press is used after stirring Filtered, obtain filtrate six and filter residue six;
S8, the filter residue six in step S7 is transferred in another reactor, and adds dust technology, using pressure after stirring Filter is filtered, and obtains filtrate seven and filter residue seven;
S9, filtrate six added into electrolytic cell be electrolysed, remove the hydrochloric acid in water, obtain a small amount of lead zinc mud, chlorine and Water, water can be as the pure water circulation uses in step S7;
S10, the filtrate seven in step S8 is added into another electrolytic cell be electrolysed, obtain chlorine and nitric acid (in water still Retain nitric acid), nitric acid can recycle as the dust technology in step S8, and it is thick that filter residue seven is dried into the obtained ferric phosphate of dehydration Product;
S11, the ferric phosphate crude product in step S8 can be prepared into battery-grade iron phosphate by roasting.
Preferably, the filter residue three in the step S2 is lead cadmia, and lead cadmia drying and dehydrating can be prepared into lead zinc raw material, filter Liquid three is solution of ferrous chloride, and solution of ferrous chloride is carried out into distillation can prepare frerrous chloride solid.
Preferably, obtained chlorine can be passed directly into sodium hydroxide solution and can prepare in the step S9 and step S10 Sodium hypochlorite.
Preferably, the rotating speed of agitator is 200r/min-400r/min in reactor in the step S1-S8.
Preferably, reactor internal temperature is set to 50 DEG C -60 DEG C in the step S1-S8.
Preferably, the sintering temperature in the step S11 is 300 DEG C -500 DEG C.
Preferably, the heavy metal sewage sludge is heavy metal spent acid sludge either useless phosphorus body refuse sludge or waste phosphoric acid sludge.
The technique effect and advantage of the present invention:One kind provided by the invention is prepared using heavy metal sewage sludge and heavy metal spent acid The method of battery-grade iron phosphate, compared with traditional preparation technology, produced in the present invention without sulfur dioxide, and the ferric phosphate prepared In be free of iron oxide and chlorion, quality is higher, and fe short circuit problem is not present in thus obtained ferric phosphate lithium cell, can be real Existing fast charge.New energy materialses are converted using solid waste, local environment pollution problem is solved, high-quality ferric phosphate can also be made, Promote the sustainable development of Steel Wire Products Industry, reduce the production cost of new energy materialses, while can be from iron oxide waste material Elementary lead zinc raw material is prepared, frerrous chloride and sodium hypochlorite can also be made, be advantageous to popularize.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not For limiting the present invention.Based on the embodiment in the present invention, those of ordinary skill in the art are not before creative work is made The every other embodiment obtained is put, belongs to the scope of protection of the invention.
Embodiment 1
A kind of method for preparing battery-grade iron phosphate using heavy metal sewage sludge and heavy metal spent acid, comprises the following steps:
S1, by iron oxide waste material add reactor in, and add spent acid regulation pH value 2, filter press is used after stirring Filtered, filter residue one and filtrate one is made;
S2, filter residue one in step S1 added in reactor, and add phosphoric acid and hydrochloric acid regulation pH value 3, after stirring reaction Filtered using filter press, filter residue two and filtrate two is made;
S3, filtered after sodium sulfide solution stirring reaction will be added in filtrate one, filter residue three and filtrate three is made;
S4, filter residue two in step S2 added in reactor, and add running water cleaning and filtered, obtain the He of filter residue four Filtrate four, filter residue four can direct harmless emission, filtrate four can recycle as the spent acid in step S1;
Filtrate two is added in distillation still by S5 is distilled with heat steam heating, obtains residue and to steam hydrochloric acid molten Liquid, hydrochloric acid solution can recycle as the hydrochloric acid in step S2;
S6, the residue in step S5 added in reactor, and add running water, entered after stirring using filter press Row filtering, obtains filtrate five and filter residue five, filtrate five can recycle as the spent acid in step S1;
S7, the filter residue five in step S6 is transferred in reactor, and adds pure water, filter press is used after stirring Filtered, obtain filtrate six and filter residue six;
S8, the filter residue six in step S7 is transferred in another reactor, and adds dust technology, using pressure after stirring Filter is filtered, and obtains filtrate seven and filter residue seven;
S9, filtrate six added into electrolytic cell be electrolysed, remove the hydrochloric acid in water, obtain a small amount of lead zinc mud, chlorine and Water, water can be as the pure water circulation uses in step S7;
S10, the filtrate seven in step S8 is added into another electrolytic cell be electrolysed, obtain chlorine and nitric acid (in water still Retain nitric acid), nitric acid can recycle as the dust technology in step S8, and it is thick that filter residue seven is dried into the obtained ferric phosphate of dehydration Product;
S11, the ferric phosphate crude product in step S8 can be prepared into battery-grade iron phosphate by roasting
Specifically, the filter residue three in the step S2 is lead cadmia, lead cadmia drying and dehydrating can be prepared into lead zinc raw material, filtered Liquid three is solution of ferrous chloride, and solution of ferrous chloride is carried out into distillation can prepare frerrous chloride solid.
Specifically, obtained chlorine can be passed directly into preparation time chlorine in sodium hydroxide solution in the step S6 and step S7 Sour sodium.
Specifically, the rotating speed of agitator is 200r/min in reactor in the step S1-S8.
Specifically, reactor internal temperature is set to 50 DEG C in the step S1-S8.
Specifically, the sintering temperature in the step S11 is 300 DEG C.
Specifically, the heavy metal sewage sludge is heavy metal spent acid sludge either useless phosphorus body refuse sludge or waste phosphoric acid sludge.
Embodiment 2
A kind of method for preparing battery-grade iron phosphate using heavy metal sewage sludge and heavy metal spent acid, comprises the following steps:
S1, add in reactor by heavy metal-polluted S1, by iron oxide waste material, and add spent acid regulation pH value 2.5, stirring is equal Filtered after even using filter press, filter residue one and filtrate one is made;
S2, filter residue one in step S1 added in reactor, and add phosphoric acid and hydrochloric acid regulation pH value 3.5, stirring reaction Filtered afterwards using filter press, filter residue two and filtrate two is made;
S3, filtered after sodium sulfide solution stirring reaction will be added in filtrate one, filter residue three and filtrate three is made;
S4, filter residue two in step S2 added in reactor, and add running water cleaning and filtered, obtain the He of filter residue four Filtrate four, filter residue four can direct harmless emission, filtrate four can recycle as the spent acid in step S1;
Filtrate two is added in distillation still by S5 is distilled with steam heating, is obtained residue and is steamed hydrochloric acid solution, Hydrochloric acid solution can recycle as the hydrochloric acid in step S2;
S6, the residue in step S5 added in reactor, and add running water, entered after stirring using filter press Row filtering, obtains filtrate five and filter residue five, filtrate five can recycle as the spent acid in step S1;
S7, the filter residue five in step S6 is transferred in reactor, and adds pure water, filter press is used after stirring Filtered, obtain filtrate six and filter residue six;
S8, the filter residue six in step S7 is transferred in another reactor, and adds dust technology, using pressure after stirring Filter is filtered, and obtains filtrate seven and filter residue seven;
S9, filtrate six added into electrolytic cell be electrolysed, remove the hydrochloric acid in water, obtain a small amount of lead zinc mud, chlorine and Water, water can be as the pure water circulation uses in step S7;
S10, the filtrate seven in step S8 is added into another electrolytic cell be electrolysed, obtain chlorine and nitric acid (in water still Retain nitric acid), nitric acid can recycle as the dust technology in step S8, and it is thick that filter residue seven is dried into the obtained ferric phosphate of dehydration Product;
S11, the ferric phosphate crude product in step S8 can be prepared into battery-grade iron phosphate by roasting.
Specifically, the filter residue three in the step S2 is lead cadmia, lead cadmia drying and dehydrating can be prepared into lead zinc raw material, filtered Liquid three is solution of ferrous chloride, and solution of ferrous chloride is carried out into distillation can prepare frerrous chloride solid.
Specifically, obtained chlorine can be passed directly into sodium hydroxide solution and can prepare in the step S9 and step S10 Sodium hypochlorite.
Specifically, the rotating speed of agitator is 300r/min in reactor in the step S1-S8.
Specifically, reactor internal temperature is set to 55 DEG C in the step S1-S8.
Specifically, the sintering temperature in the step S11 is 400 DEG C.
Specifically, the heavy metal sewage sludge is heavy metal spent acid sludge either useless phosphorus body refuse sludge or waste phosphoric acid sludge.
Embodiment 3
A kind of method for preparing battery-grade iron phosphate using heavy metal sewage sludge and heavy metal spent acid, comprises the following steps:
S1, by iron oxide waste material add reactor in, and add spent acid regulation pH value 3, filter press is used after stirring Filtered, filter residue one and filtrate one is made;
S2, filter residue one in step S1 added in reactor, and add phosphoric acid and hydrochloric acid regulation pH value 4, after stirring reaction Filtered using filter press, filter residue two and filtrate two is made;
S3, filtered after sodium sulfide solution stirring reaction will be added in filtrate one, filter residue three and filtrate three is made;
S4, filter residue two in step S2 added in reactor, and add running water cleaning and filtered, obtain the He of filter residue four Filtrate four, filter residue four can direct harmless emission, filtrate four can recycle as the spent acid in step S1;
Filtrate two is added in distillation still by S5 is distilled with heat steam heating, obtains residue and to steam hydrochloric acid molten Liquid, hydrochloric acid solution can recycle as the hydrochloric acid in step S2;
S6, the residue in step S5 added in reactor, and add running water, entered after stirring using filter press Row filtering, obtains filtrate five and filter residue five, filtrate five can recycle as the spent acid in step S1;
S7, the filter residue five in step S6 is transferred in reactor, and adds pure water, filter press is used after stirring Filtered, obtain filtrate six and filter residue six;
S8, the filter residue six in step S7 is transferred in another reactor, and adds dust technology, using pressure after stirring Filter is filtered, and obtains filtrate seven and filter residue seven;
S9, filtrate six added into electrolytic cell be electrolysed, remove the hydrochloric acid in water, obtain a small amount of lead zinc mud, chlorine and Water, water can be as the pure water circulation uses in step S7;
S10, the filtrate seven in step S8 is added into another electrolytic cell be electrolysed, obtain chlorine and nitric acid (in water still Retain nitric acid), nitric acid can recycle as the dust technology in step S8, and it is thick that filter residue seven is dried into the obtained ferric phosphate of dehydration Product;
S11, the ferric phosphate crude product in step S8 can be prepared into battery-grade iron phosphate by roasting
Specifically, the filter residue three in the step S2 is lead cadmia, lead cadmia drying and dehydrating can be prepared into lead zinc raw material, filtered Liquid three is solution of ferrous chloride, and solution of ferrous chloride is carried out into distillation can prepare frerrous chloride solid.
Specifically, obtained chlorine can be passed directly into sodium hydroxide solution and can prepare in the step S9 and step S10 Sodium hypochlorite.
Specifically, the rotating speed of agitator is 400r/min in reactor in the step S1-S8.
Specifically, reactor internal temperature is set to 60 DEG C in the step S1-S8.
Specifically, the sintering temperature in the step S11 is 500 DEG C.
Specifically, the heavy metal sewage sludge is heavy metal spent acid sludge either useless phosphorus body refuse sludge or waste phosphoric acid sludge.
In summary:It is provided by the invention a kind of to prepare battery-grade iron phosphate using heavy metal sewage sludge and heavy metal spent acid Method, compared with traditional preparation technology, produced in the present invention without sulfur dioxide, and iron oxide is free of in the phosphoric acid ferro-aluminum prepared And chlorion, optimize aluminum phosphate iron cell fast charge effect, the content of ferric phosphate is higher, and new energy materialses, solution are converted using solid waste Determine local environment pollution problem, promoted the sustainable development of Steel Wire Products Industry, while lead can be prepared from heavy metal sewage sludge Zinc raw material, ferrous oxide and sodium hypochlorite, be advantageous to popularize.
Finally it should be noted that:The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic, Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., it should be included in the present invention's Within protection domain.

Claims (7)

  1. A kind of 1. method for preparing battery-grade iron phosphate using heavy metal sewage sludge and heavy metal spent acid, it is characterised in that including such as Lower step:
    S1, by iron oxide waste material add reactor in, and add spent acid regulation pH value, carried out after stirring using filter press Filter, filter residue one and filtrate one is made;
    S2, filter residue one in step S1 added in reactor, and add phosphoric acid and hydrochloric acid regulation pH value, using pressure after stirring reaction Filter is filtered, and filter residue two and filtrate two is made;
    S3, filtered after vulcanized sodium or useless sodium sulfide solution stirring reaction will be added in filtrate one, filter residue three and filtrate is made Three;
    S4, filter residue two in step S2 added in reactor, and add running water cleaning and filtered, obtain filter residue four and filtrate Four, filter residue four can direct harmless emission, filtrate four can recycle as the spent acid in step S1;
    Filtrate two is added in distillation still by S5 is distilled with heat steam heating, is obtained residue and is steamed hydrochloric acid solution, salt Acid solution can recycle as the hydrochloric acid in step S2;
    S6, the residue in step S5 added in reactor, and add running water, carried out after stirring using filter press Filter, obtains filtrate five and filter residue five, filtrate five can recycle as the spent acid in step S1;
    S7, the filter residue five in step S6 is transferred in reactor, and adds pure water, carried out after stirring using filter press Filtering, obtains filtrate six and filter residue six;
    S8, the filter residue six in step S7 is transferred in another reactor, and adds dust technology, filter press is used after stirring Filtered, obtain filtrate seven and filter residue seven;
    S9, filtrate six is added into electrolytic cell be electrolysed, removed the hydrochloric acid in water, obtain a small amount of lead zinc mud, chlorine and water, water Can be as the pure water circulation use in step S7;
    S10, the filtrate seven in step S8 is added into another electrolytic cell be electrolysed, obtained chlorine and nitric acid (still retains in water Nitric acid), nitric acid can recycle as the dust technology in step S8, and filter residue seven is dried into dehydration is made ferric phosphate crude product;
    S11, the ferric phosphate crude product in step S8 can be prepared into battery-grade iron phosphate by roasting.
  2. A kind of 2. side that battery-grade iron phosphate is prepared using heavy metal sewage sludge and heavy metal spent acid according to claim 1 Method, it is characterised in that:Filter residue three in the step S2 is lead cadmia, and lead cadmia drying and dehydrating can be prepared into lead zinc raw material, filter Liquid three is solution of ferrous chloride, and solution of ferrous chloride is carried out into distillation can prepare frerrous chloride solid.
  3. A kind of 3. side that battery-grade iron phosphate is prepared using heavy metal sewage sludge and heavy metal spent acid according to claim 1 Method, it is characterised in that:Obtained chlorine, which can be passed directly into sodium hydroxide solution, in the step S9 and step S10 prepares time chlorine Sour sodium.
  4. A kind of 4. side that battery-grade iron phosphate is prepared using heavy metal sewage sludge and heavy metal spent acid according to claim 1 Method, it is characterised in that:The rotating speed of agitator is 200r/min-400r/min in reactor in the step S1-S8.
  5. A kind of 5. side that battery-grade iron phosphate is prepared using heavy metal sewage sludge and heavy metal spent acid according to claim 1 Method, it is characterised in that:Reactor internal temperature is set to 50 DEG C -60 DEG C in the step S1-S8.
  6. A kind of 6. side that battery-grade iron phosphate is prepared using heavy metal sewage sludge and heavy metal spent acid according to claim 1 Method, it is characterised in that:Sintering temperature in the step S11 is 300 DEG C -500 DEG C.
  7. A kind of 7. side that battery-grade iron phosphate is prepared using heavy metal sewage sludge and heavy metal spent acid according to claim 1 Method, it is characterised in that:The heavy metal sewage sludge is heavy metal spent acid sludge either useless phosphorus body refuse sludge or waste phosphoric acid sludge.
CN201710845301.8A 2017-09-19 2017-09-19 Method for preparing battery-grade iron phosphate by using heavy metal sludge Active CN107611433B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108313996A (en) * 2018-03-29 2018-07-24 宁夏滨河新材料科技有限公司 The method for producing battery-grade anhydrous iron phosphate using pyrite cinder
CN108609594A (en) * 2018-03-29 2018-10-02 宁夏滨河新材料科技有限公司 The method that wastewater treatment recycles in ferric phosphate production
CN110357058A (en) * 2019-08-12 2019-10-22 江苏荣信环保科技有限公司 The method that ferric phosphate is made in phosphorous metal sludge and spent acid
CN111825069A (en) * 2020-06-08 2020-10-27 湖南雅城新材料有限公司 Method for preparing flaky iron phosphate by utilizing acid waste liquid and calcium phosphate waste residue
CN112047319A (en) * 2020-09-11 2020-12-08 南昌航空大学 Method for recovering battery-grade iron phosphate from waste iron phosphate slag

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CN101481104A (en) * 2009-02-11 2009-07-15 刘世琦 Method for producing high purity battery level ferric pyrophosphate from pickle liquor
CN104609615A (en) * 2015-02-13 2015-05-13 江苏艾特克环境工程设计研究院有限公司 Heavy-metal-containing surface treatment wastewater treatment method
CN105692576A (en) * 2016-03-10 2016-06-22 三峡大学 Method for preparing battery-grade FePO4 from industrial iron-containing waste

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101481104A (en) * 2009-02-11 2009-07-15 刘世琦 Method for producing high purity battery level ferric pyrophosphate from pickle liquor
CN104609615A (en) * 2015-02-13 2015-05-13 江苏艾特克环境工程设计研究院有限公司 Heavy-metal-containing surface treatment wastewater treatment method
CN105692576A (en) * 2016-03-10 2016-06-22 三峡大学 Method for preparing battery-grade FePO4 from industrial iron-containing waste

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108313996A (en) * 2018-03-29 2018-07-24 宁夏滨河新材料科技有限公司 The method for producing battery-grade anhydrous iron phosphate using pyrite cinder
CN108609594A (en) * 2018-03-29 2018-10-02 宁夏滨河新材料科技有限公司 The method that wastewater treatment recycles in ferric phosphate production
CN108313996B (en) * 2018-03-29 2021-04-20 宁夏滨河新材料科技有限公司 Method for preparing battery-grade anhydrous iron phosphate by using sulfuric acid cinder
CN108609594B (en) * 2018-03-29 2021-08-17 宁夏滨河新材料科技有限公司 Method for treating and recycling wastewater in iron phosphate production
CN110357058A (en) * 2019-08-12 2019-10-22 江苏荣信环保科技有限公司 The method that ferric phosphate is made in phosphorous metal sludge and spent acid
CN111825069A (en) * 2020-06-08 2020-10-27 湖南雅城新材料有限公司 Method for preparing flaky iron phosphate by utilizing acid waste liquid and calcium phosphate waste residue
CN112047319A (en) * 2020-09-11 2020-12-08 南昌航空大学 Method for recovering battery-grade iron phosphate from waste iron phosphate slag

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