CN110342485A - A kind of battery-grade iron phosphate alkali-free formula production method - Google Patents
A kind of battery-grade iron phosphate alkali-free formula production method Download PDFInfo
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- CN110342485A CN110342485A CN201910719356.3A CN201910719356A CN110342485A CN 110342485 A CN110342485 A CN 110342485A CN 201910719356 A CN201910719356 A CN 201910719356A CN 110342485 A CN110342485 A CN 110342485A
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- ferric phosphate
- phosphate
- alkali
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 85
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 50
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 46
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 46
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 38
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 31
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 31
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000012452 mother liquor Substances 0.000 claims abstract description 20
- 239000000047 product Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 239000006227 byproduct Substances 0.000 claims abstract description 12
- 239000007791 liquid phase Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000005086 pumping Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000013049 sediment Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 230000007246 mechanism Effects 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011260 aqueous acid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000001117 sulphuric acid Substances 0.000 abstract description 5
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 26
- 239000000463 material Substances 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 10
- 238000006386 neutralization reaction Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000002699 waste material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000004254 Ammonium phosphate Substances 0.000 description 3
- 235000019289 ammonium phosphates Nutrition 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of battery-grade iron phosphate alkali-free formula production methods, the present invention produces mother liquor complete alternation technique using ferric phosphate, with the pure iron stick of mass percent 99.95% and the mother liquor of 12%~16% byproduct of reaction sulfuric acid containing mass percent in 45 DEG C of successive reaction 8h~12h, ferrous sulfate solution is generated；By ferrous sulfate solution pumping to reaction kettle, excessive phosphoric acid,diluted aqueous solution is added under normal temperature and pressure state, generate sediment ferric phosphate and dilute sulfuric acid, after being cooled and separated step, solid formation ferric phosphate is gone into washing, drying process, liquid phase object sulfuric acid, phosphoric acid all return to ferrous sulfate preparation section, so on circulate, to save the consumption of raw material sulphuric acid and phosphoric acid, go to neutralize acid mother liquid without alkaline matter.The present invention have reduce raw materials consumption and reduce cost for wastewater treatment advantage, the particle diameter distribution of ferric phosphate battery product is uniform, electrical performance indexes more preferably, with good economic efficiency and environmental benefit.
Description
Technical field
The invention belongs to new-energy automobile dynamic lithium battery material manufacture technical fields, particularly relate to a kind of battery
Grade ferric phosphate alkali-free formula production method.
Background technique
At present in new-energy automobile dynamic lithium battery industry, developing low-cost long-life batteries and can safely and fast it fill
Battery is two big key technologies.Ferric phosphate lithium cell has been achieved with obviously in charge and discharge number and charging security technical aspect
The main reason for breaking through, but its major defect is that battery cost is high, and causing battery at high cost be positive electrode at
This is higher.Ferric phosphate is the upstream key persursor material of ferric phosphate lithium cell, so, the cost to reduction lithium battery is necessary
It is picked up from source, battery industry currently realizes LiFePO 4 material cost using the method for cost is forced in the prior art
Reduced target forces upstream persursor material ferric phosphate to research and develop new technology to solve the problems, such as that product cost is higher.
In the traditional technology of existing ferric phosphate production, there are two types of major processes: first is that outsourcing titanium dioxide industry pair
The ferrous sulfate of production synthesizes ferric phosphate with phosphoric acid, although this technique can reduce the part material cost of phosphoric acid iron product, after
Continuous process requirement adds alkali to neutralize a large amount of sulfuric acid and phosphoric acid of production process generation, and the discharge for eventually leading to high slat-containing wastewater is asked
The expense of topic, processing waste water does not support the cost of raw material reduction, therefore can not reach the purpose of drop sheet.Second is that iron phosphorus synthetic method
Process route, i.e. pure iron are reacted with dilute sulfuric acid is made ferrous sulfate, then synthesizes ferric phosphate with phosphoric acid.This method and the first side
The advantages of method compares is that product impurity is few, purity is high.But the aqueous sulfuric acid that reaction process generates, which still needs, to be gone with alkali
It is still very high with the cost of, brine waste processing, so still can not fundamentally reduce the cost of product.
Summary of the invention
The present invention in order to overcome the deficiencies in the prior art, provide one kind can effectively save resource, simple flow,
The battery-grade iron phosphate alkali-free formula production method of low production cost.
The present invention is achieved by the following technical solutions: a kind of battery-grade iron phosphate alkali-free formula production method, the production
For method using ferric phosphate production mother liquor complete alternation without alkali pretreatment, battery-grade iron phosphate prepares the work of ferric phosphate using pure iron method
Skill, the process that the acid mother liquid generated in ferric phosphate synthetic reaction process returns to before reaction are recycled, and ferric phosphate is raw
Mother liquor complete alternation is produced in molten ironworker's sequence, is no longer needed to in alkaline matter and by-product sulfate liquor, to realize that alkali-free formula is raw
Production method is saved one of important procedure, and is generated without brine waste, without construction wastewater treatment equipment.
Battery-grade iron phosphate alkali-free formula production method of the present invention specifically comprises the following steps:
A, the mother for the pure iron stick and 12%~16% byproduct of reaction sulfuric acid containing mass percent for being 99.95% with mass percent
Liquid generates ferrous sulfate solution, the reaction mechanism is as follows in 42 DEG C~48 DEG C successive reaction 8h~12h:
H2SO4+ Fe=FeSO4+ H2↑；
B, by the ferrous sulfate solution pumping in step a to reaction kettle, excessive dilute phosphorus is added after being warming up to 40 DEG C~48 DEG C
Aqueous acid, the ferrous sulfate solution containing micro ferric phosphate nucleus carry out homogeneous liquid phase with phosphate aqueous solution and react, and room temperature is normal
Reaction generates evengranular sediment ferric phosphate and dilute sulfuric acid under pressure condition, and the partial size of phosphoric acid iron precipitate is convenient for solid-liquid point
From, meet downstream client production ferric phosphate lithium cell electrical performance indexes promotion, the reaction mechanism is as follows:
2 FeSO4+ 2 H3PO4 + H202 = 2 FeP04·H2The H of O ↓+22SO4；
C, after cooling and separating step, by solid formation ferric phosphate successively by washing, dry and de- crystallization water process, thus
To battery-grade iron phosphate product.Liquid phase object sulfate liquor all returns in ferrous sulfate preparation section, so on circulate, thus
The consumption of alkaline matter needed for saving the consumption and the subsequent neutralization of acid mother liquid of raw material sulphuric acid and phosphoric acid.
In step a, the pure iron stick and contain mass percent 13%~15% instead that mass percent is 99.95% are preferably used
Answer the mother liquor of by-product sulfuric acid in 45 DEG C of successive reaction 10h.
In stepb, by the ferrous sulfate solution pumping in step a to reaction kettle, 42 DEG C~48 DEG C are preferably warming up to
After excessive phosphoric acid,diluted aqueous solution is added.
Alkaline matter is ammonium hydroxide or caustic soda, and it includes sulfuric acid and phosphoric acid that ferric phosphate, which produces in mother liquor, in step c, liquid phase object
It include excessive phosphoric acid in sulfate liquor.
The present invention produces mother liquor complete alternation technique using ferric phosphate, with the pure iron stick of mass percent 99.95% and containing matter
12%~16% sulfuric acid solution of percentage is measured in 45 DEG C or so successive reaction 8h~12h, generates ferrous sulfate solution；By sulfuric acid Asia
Excessive phosphoric acid,diluted aqueous solution is added to reaction kettle in ferrous solution pumping under normal temperature and pressure state, generate sediment ferric phosphate and
Solid formation ferric phosphate after being cooled and separated step, is gone washing, drying process, liquid phase object sulfuric acid, phosphoric acid all return by dilute sulfuric acid
Ferrous sulfate preparation section is returned, so on circulate, to save the consumption of raw material sulphuric acid and phosphoric acid, is gone without alkaline matter
And acid mother liquid.
Innoxious wastewater processing technology and the even phase reaction upgrading technology of liquid are also applied in production method of the invention.Nothing
Evilization wastewater processing technology: the process that reaction mother liquor returns before reaction is recycled, and is not necessarily to alkaline matter to reaction
By-product sulfuric acid waste liquor is neutralized, to form a kind of innoxious wastewater processing technology.The even phase reaction upgrading of liquid
Technology: carrying out homogeneous liquid phase with phosphoric acid solution with the ferrous sulfate solution containing micro ferric phosphate nucleus and react, and it is equal to generate particle
Even phosphoric acid iron precipitate, type looks consistency is good, more meets downstream lithium iron phosphate positive material industry and refers to product cut size technology
Target requirement, convenient for being separated by solid-liquid separation.
The beneficial effects of the present invention are: the invention belongs to a kind of environmentally protective manufacturing technology of battery-grade iron phosphate, this hair
The bright liquid product ferrous sulfate reacted by pure iron stick with reuse dilution heat of sulfuric acid is reacted with phosphoric acid solution again is made phosphoric acid
Iron and technical process need not use the process of alkali neutralization.Specific practice of the invention is generated using ferric phosphate synthetic reaction
Mother liquor, which carries out reacting with pure iron stick under a certain concentration, generates ferrous sulfate solution, this solution obtains ferric phosphate with phosphatase reaction again
Finished product, thus realize reaction mother liquor complete alternation, the subsequent neutralisation treatment of sulfuric acid for avoiding reaction from generating.The technology back that the present invention studies
Scape is, to reduce environmental pollution, to shorten process flow from the target for reducing battery-grade iron phosphate product cost, economize on resources
Consumption is innovative point, belongs to green manufacturing technology, and technical application has a extensive future, and will be reduced for new energy car battery industry
Persursor material cost, the promotion market competitiveness play key effect.
Alkali-free technique production method in the present invention had not only saved the consumption of raw material sulphuric acid, but also reduced needed for subsequent processing
The consumption of alkaline matter there is drop compared with the of the same trade titaniferous ferrous sulfate phosphoric acid method being commonly used in the prior art
Low raw materials consumption and the advantage for reducing cost for wastewater treatment, while the particle diameter distribution of phosphoric acid iron product is uniform, is produced with this method
Ferric phosphate for cell positive material production battery electrical property index more preferably so that required by cell positive material industry
Product comprehensive quality is more excellent, embodies technically with good economic efficiency and environmental benefit.
The present invention has the further advantage that the process route and raw material proportioning advanced design of the 1, technology, fully demonstrates
There are obvious comparative advantages, domestic ferric phosphate rows for the utilization of resources and saving, the unit cost of production and conventional process techniques of the same trade
Industry not yet forms such available technology, belongs to original innovation technology；2, overall technology highway route design has fully considered environmental protection
Function reduces pollutant discharge amount, meets green manufacture technology scope；3, product granularity is uniform, and partial size meets down-stream enterprise and makes
With standard, the product cost advantage produced using the technology is obvious, so that reducing being implemented as lithium battery material cost objective
May, it is more competitive in similar product market；4, technology implementation success example illustrates that Technological Economy value is good, more traditional
Technology more has industrialization prospect；5, part process is simplified, opposite to have saved construction investment.
Detailed description of the invention
Fig. 1 is traditional handicraft one: ferrous sulfate synthesizes the production procedure schematic diagram of ferric phosphate with phosphoric acid；
Fig. 2 is traditional handicraft two: the production procedure schematic diagram of iron phosphorus synthetic method process route；
Fig. 3 is the production procedure schematic diagram of battery-grade iron phosphate alkali-free formula production method of the present invention.
Specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
As shown in figure 3, a kind of battery-grade iron phosphate alkali-free formula production method, which produces mother liquor using ferric phosphate
Complete alternation prepares the technique of ferric phosphate, ferric phosphate synthetic reaction process using pure iron method without alkali pretreatment, battery-grade iron phosphate
Molten ironworker's sequence that the acid mother liquid of middle generation returns to before reaction recycles, by ferric phosphate production mother liquor complete alternation in molten iron
In process, no longer need to be saved important together with by-product sulfate liquor to realize alkali-free formula production method in alkaline matter
Process, and generated without brine waste, without construction wastewater treatment equipment.
Production method of the invention specifically comprises the following steps:
A, the mother for the pure iron stick and 12%~16% byproduct of reaction sulfuric acid containing mass percent for being 99.95% with mass percent
Liquid generates ferrous sulfate solution, the reaction mechanism is as follows in 42 DEG C~48 DEG C successive reaction 8h~12h:
H2SO4+ Fe=FeSO4+ H2↑；
B, by the ferrous sulfate solution pumping in step a to reaction kettle, excessive dilute phosphorus is added after being warming up to 40 DEG C~48 DEG C
Aqueous acid, the ferrous sulfate solution containing micro ferric phosphate nucleus carry out homogeneous liquid phase with phosphate aqueous solution and react, and room temperature is normal
Reaction generates evengranular sediment ferric phosphate and dilute sulfuric acid under pressure condition, and the partial size of phosphoric acid iron precipitate is convenient for solid-liquid point
From, meet downstream client production ferric phosphate lithium cell electrical performance indexes promotion, the reaction mechanism is as follows:
2 FeSO4+ 2 H3PO4 + H202 = 2 FeP04·H2The H of O ↓+22SO4；
C, after cooling and separating step, by solid formation ferric phosphate successively by washing, dry and de- crystallization water process, thus
To battery-grade iron phosphate product, liquid phase object sulfate liquor is all returned in ferrous sulfate preparation section, so on circulate, thus
The consumption of alkaline matter needed for saving the consumption and the subsequent neutralization of acid mother liquid of raw material sulphuric acid and phosphoric acid.
In step a, the pure iron stick and contain mass percent 13%~15% instead that mass percent is 99.95% are preferably used
Answer the mother liquor of by-product sulfuric acid in 45 DEG C of successive reaction 10h.
In stepb, by the ferrous sulfate solution pumping in step a to reaction kettle, 42 DEG C~48 DEG C are preferably warming up to
After excessive phosphoric acid,diluted aqueous solution is added.
Alkaline matter is ammonium hydroxide or caustic soda, and it includes sulfuric acid and phosphoric acid that ferric phosphate, which produces in mother liquor, in step c, liquid phase object
It include excessive phosphoric acid in sulfate liquor.
Embodiment: by production method of the invention using Mr. Yu's dynamic lithium battery persursor material 2 × 5000t/a's of enterprise
In battery-grade iron phosphate project, which has been built up using the Innovative process technology in the present invention in October, 2018 a set of
The battery-grade iron phosphate alkali-free formula process units of 5000t/a, commissioning test run in November, it is reachable that device technique appraises and decides production capacity
5000t/a appraises and decides a day production capacity 15.15t/d, and the actual production from March, 2018 to 2 months 2019 is about 4868.2t, average day
Yield about 14.75t/d, device capbility utilization rate is 97.36% during production.
The present invention is calculated in terms of three below to battery-grade iron phosphate enterprise bring comprehensive benefit:
1, the theoretical value of sulfuric acid saving is calculated according to reaction equation
2 FeSo4 + 2 H3PO4 + H202 = 2 FeP04·H2O↓ + 2 H2SO4
304 196 34 338 196
Y 4868.2*99.5% X1
It solves: the sulfuric acid X of generation1=(4868.2 × 99.5% × 196)/338=2808.865t(100%)；
Ferrous sulfate amount Y=(4868.2 × 99.5% × 304)/338=4356.60t(100% needed).
It is equivalent to 98% sulfuric acid quantity of goods produced X=2808.865/98%=2866.189 (t), uses X1Sulfuric acid fully recovering
In the preparation of ferrous sulfate, the ferrous sulfate that theoretically can produce is Y1, then:
H2SO4+ Fe=FeSO4+ H2↑
98 152 2
2808.865 Y1
It solves: Y1=2808.865×152/98=4356.6(t)。Y1=Y illustrates that reuse sulfuric acid amount is theoretically fully able to meet
Ferrous sulfate amount needed for 4868.2t ferric phosphate yield, it was demonstrated that mother liquor is all recycled and can be dissolved, the sulfuric acid amount dissolved
As sulfuric acid saving 2866.189t(98% quantity of goods produced).
2, waste liquor neutralisation treatment ammonium hydroxide consumption
By traditional handicraft, if not having to Recycling Mother Solution technology, ferric phosphate synthetic reaction by-product sulfuric acid and excess phosphoric acid are assumed to use
It is discharged after 20% ammonium hydroxide neutralisation treatment, treatment mechanism is as follows:
(1) H2SO4+ 2 NH3·H2O=(NH4)2SO4+ 2 H2O
98 70 132 36
2808.865 Z A1 B1
Solve: Z=(2808.865 × 70)/98=2006.332 (t) (100%) converts into 20% ammonium hydroxide quantity of goods produced Z1=
2006.332/20%=10031.66 (t).
Neutralization reaction generates ammonium sulfate A1=2808.865×132/98=3783.37(t)；
Generate water B1=2808.865×36/98=1031.83(t)。
(2) assume that excess phosphoric acid is the 10% of theoretical consumption,
It is reacted according to step 1, theoretical phosphoric acid annual consumption=4868.2 × 99.5% × 196/338=2808.865t/a, neutralizes institute
The ammonia vol needed is Z2:
H3PO4 + 3 NH3·H2O = (NH4)3PO4+ 3H2O
98 105 131 54
2808.865 × 110% Z2 A2 B2
It solves: Z2=(2808.865 × 110% × 105)/98=3310.45 (t) (100%) converts into 20% ammonium hydroxide quantity of goods produced Z3=
3310.45/20%=16552.25 (t).
Neutralization reaction generates ammonium phosphate A2=2808.865 × 110% × 131/98=4130.18 (t)；
Generate water B1=2808.865 × 110% × 36/98=1702.52 (t).
Above (1), (2) item year need to 20% ammonium hydroxide total amount be 26583.91 (t).
3, Economic Efficiency
The present invention is compared with traditional handicraft compared with following innovative technology value:
1) sulfuric acid raw material saving is worth
98% sulfuric acid price is to save value in year to 500 yuan/t of factory's average price in the market in enterprise location are as follows: 2808.865t/a ×
500 yuan/t=1404432.5 yuan/a.
2) it neutralizes and is worth with the saving of alkali
20% food-grade ammonium hydroxide price is to save value in year to 1000 yuan/t of the price at factory currently on the market are as follows: 26583.91t/a ×
1000 yuan/t=26583910 yuan/a.
3) quality-improving brings product selling price to promote 3% or so, increases product sales value are as follows:
16000 yuan/t × 3% × 4868.2t/a=2336736 yuan/a.
4) process Facilities Construction, investment reduction are reduced
The technology of the present invention is compared with other techniques of the same trade, because reducing evaporation and concentration and waste water disposal facility, builds to save
If investment 10% or so, value is saved in the investment of embodiment are as follows:
40000000 yuan (project investment in fixed assets) × 10%=4000000 yuan, share by 10 annuals, then embodies valence every year
Value is 400000 yuan/a.
5) because reducing sewage yield, charges for disposing pollutants are saved
Traditional handicraft consumption washing desalted water 16m per ton3/ t needs to consume desalted water based on 4868.2t/a yield
77891.2m3/ t, wherein being 3783.37t/a because neutralizing the ammonium sulfate (salt) generated, generating ammonium phosphate (salt) is 4130.18t/
A, it is 1031.83+1702.52=2734.35t/a that reaction, which generates water,.
Waste water generates total amount=washing water+raw material and brings water+reaction generation water+ammonium salt=washing water 77891.2+(phosphoric acid band into
Enter 870.28+ sulfuric acid bring into 56.18+ ammonium hydroxide bring into 21267.13+ hydrogen peroxide bring into 2190.7)+reaction generate water 2734.35+
Ammonium sulfate 3783.37+ 4130.18=112923.39t/a of ammonium phosphate, waste water salt content 7.0% or so.
If after implementing the mother liquor complete alternation alkali-free technique in the present invention, slurry amount reduces desalination water consumption 50%,
And bring water into without ammonium hydroxide, neutralization reaction generates water and various ammonium salts, then sewage yield=[ washing water 77891.2 × 50%
+ (phosphoric acid bring 870.28+ sulfuric acid into bring 56.18+ hydrogen peroxide into bring 2190.7 into) ]=42062.76 (t/a), waste water saliferous is 0.
The present invention compared with traditional handicraft compared with: reduce wastewater discharge=112923.39-42062.76=70860.63t/a；
Save sewage treatment expense=70860.63t/a × 15 yuan/t=1062909.45 yuan/a；
Save desalted water expense=77891.2 × 50%t/a × 10 yuan/a=389456 yuan/a；
Location Environmental Protection Agency, enterprise charges for disposing pollutants fee-collection standard is 1.5 yuan/m3, project saving charges for disposing pollutants are as follows: 70860.63m3/a×
1.5 yuan/m3=106290.95 yuan/a.
To sum up, since technical advance bring comprehensive benefit of the invention is total are as follows: 32283734.9 yuan/a, booth to list
Position product cost directly reduces expense=32283734.9/4868.2=6631.56 yuan/t.Thus illustrate, the technology of the present invention is practical
Product economy benefit brought by upper is considerable, can drive realize downstream lithium iron phosphate cell material cost substantially completely
Decline, while environmental benefit is also fairly obvious, thus the ferric phosphate manufacturing enterprise of this technology is used to lithium battery presoma industry
Possess apparent market competition advantage.
Finally it should be noted that the above content is merely illustrative of the technical solution of the present invention, rather than the present invention is protected
The limitation of range, the simple modification or equivalent replacement that those skilled in the art carry out technical solution of the present invention,
All without departing from the spirit and scope of technical solution of the present invention.
Claims (7)
1. a kind of battery-grade iron phosphate alkali-free formula production method, it is characterised in that: the battery-grade iron phosphate alkali-free formula producer
For method using ferric phosphate production mother liquor complete alternation without alkali pretreatment, the battery-grade iron phosphate prepares ferric phosphate using pure iron method
Technique, the process that the acid mother liquid generated in ferric phosphate synthetic reaction process returns to before reaction is recycled, by ferric phosphate
Mother liquor complete alternation is produced in molten ironworker's sequence, is no longer needed to in alkaline matter and by-product sulfate liquor, to realize alkali-free formula
Production method.
2. a kind of battery-grade iron phosphate alkali-free formula production method according to claim 1, it is characterised in that: the producer
Method specifically comprises the following steps:
A, the mother for the pure iron stick and 12%~16% byproduct of reaction sulfuric acid containing mass percent for being 99.95% with mass percent
Liquid generates ferrous sulfate solution, the reaction mechanism is as follows in 42 DEG C~48 DEG C successive reaction 8h~12h:
H2SO4+ Fe=FeSO4+ H2↑；
B, by the ferrous sulfate solution pumping in step a to reaction kettle, excessive dilute phosphorus is added after being warming up to 40 DEG C~48 DEG C
Aqueous acid, the ferrous sulfate solution containing micro ferric phosphate nucleus carry out homogeneous liquid phase with phosphate aqueous solution and react, and room temperature is normal
Reaction generates evengranular sediment ferric phosphate and dilute sulfuric acid under pressure condition, and the reaction mechanism is as follows:
2 FeSO4+ 2 H3PO4 + H202 = 2 FeP04·H2The H of O ↓+22SO4；
C, after cooling and separating step, by solid formation ferric phosphate successively by washing, dry and de- crystallization water process, thus
To battery-grade iron phosphate product, liquid phase object sulfate liquor is all returned in ferrous sulfate preparation section, so on circulate.
3. a kind of battery-grade iron phosphate alkali-free formula production method according to claim 2, it is characterised in that: in step a,
The mother liquor of the pure iron stick and 13%~15% byproduct of reaction sulfuric acid containing mass percent that are 99.95% with mass percent is 45
DEG C successive reaction 10h.
4. a kind of battery-grade iron phosphate alkali-free formula production method according to claim 2, it is characterised in that: in stepb,
It is water-soluble that excessive phosphoric acid,diluted is added by the ferrous sulfate solution pumping in step a to reaction kettle, after being warming up to 42 DEG C~48 DEG C
Liquid.
5. a kind of battery-grade iron phosphate alkali-free formula production method according to claim 1, it is characterised in that: the basic species
Matter is ammonium hydroxide or caustic soda.
6. a kind of battery-grade iron phosphate alkali-free formula production method according to claim 1, it is characterised in that: the ferric phosphate
Produce includes sulfuric acid and phosphoric acid in mother liquor.
7. a kind of battery-grade iron phosphate alkali-free formula production method according to claim 2, it is characterised in that: in step c,
It include excessive phosphoric acid in the liquid phase object sulfate liquor.
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| CN114560455A (en) * | 2022-03-08 | 2022-05-31 | 四川大学 | Method for preparing battery-grade iron phosphate by using ferrous sulfate and phosphoric acid |
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